CN105814015B

CN105814015B - The Salan catalyst that cyclopentadienyl group replaces

Info

Publication number: CN105814015B
Application number: CN201480067926.0A
Authority: CN
Inventors: M·E·艾万斯; D·A·坎奥; M·科尔; K·普里斯
Original assignee: Ramot at Tel Aviv University Ltd; Exxon Chemical Patents Inc
Current assignee: Ramot at Tel Aviv University Ltd; ExxonMobil Chemical Patents Inc
Priority date: 2013-12-13
Filing date: 2014-12-02
Publication date: 2019-04-02
Anticipated expiration: 2034-12-02
Also published as: EP3080073A1; US20150166690A1; WO2015088819A1; CN105814015A; US9290589B2; EP3080073B1; EP3080073A4

Abstract

The Salan catalyst of cyclopentadienyl group substitution is disclosed, the catalyst system comprising the Salan catalyst that activator and the cyclopentadienyl group replace, the method including contacting one or more alkene with the catalyst system, and the polymer prepared by this method.

Description

The Salan catalyst that cyclopentadienyl group replaces

Related application:

22, provisional application US 61/915,924 and 2014 on the April submitted this application claims on December 13rd, 2013 mention The equity of the provisional application US 61/982,823 of friendship, these documents are all included in the application by quoting.

Invention field

The present invention relates to Salan catalyst compounds and catalyst systems, make using the method for this catalyst, and thus Standby polymer.

Background of invention

The purposes of olefin polymerization catalysis in the industry is huge.Therefore, it is interested in find new catalyst system, mention The commercial applicability of high catalyst is simultaneously able to produce the polymer with improved property.

There is a need in the art for new and improved catalyst and catalyst system with obtain new and improved polyolefin, Polymerization etc..Therefore, there is a need in the art for the new and improved catalyst systems for olefinic polymerization, to realize spy Fixed polymer property, such as high tacticity, high molecular weight or their combination.

Summary of the invention

This disclosure relates to which catalyst compounds and the catalyst system comprising the compound, prepare the catalyst compounds With the method for system, and the method for carrying out olefinic polymerization using the catalyst compounds and system.

In a kind of embodiment according to the present invention, catalyst compounds are expressed from the next:

Wherein each solid line indicates covalent bond and each arrow indicates, and there is different degrees of valence state to match with different degrees of The key of position；

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each X¹And X²It independently is monovalent C₁-C₂₀Alkyl, the official comprising the element from periodic table of elements 13-17 race It can group or X¹And X²It is joined together to form C₄-C₆₂Cyclic annular or polycyclic ring structure, but condition is the X when M is trivalent²It does not deposit ?；

Wherein each R^*1And R^*2It independently include huge functional group, electron-withdrawing group or their combination, Yi Jiqi Middle R^*1And R^*2At least one of independently include the cyclopentadienyl group that has following structure:

Wherein C^*Indicate the connection carbon of the group；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、 R¹⁶And R¹⁷It independently is hydrogen, C₁-C₄₀ Alkyl, the functional group comprising the element from periodic table of elements 13-17 race, R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、 R¹²、R¹³、R¹⁴、 R¹⁵、R¹⁶And R¹⁷In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring knot Structure or their combination；

R⁷For C₁-C₄₀Alkyl or functional group comprising the element from periodic table of elements 13-17 race；And

Y is divalent C₁-C₂₀Alkyl.

In some embodiments according to the present invention, R^*1And R^*2At least one of independently include it is substituted or unsubstituted C₄-C₂₀Aliphatic group or substituted or unsubstituted C₄-C₂₀Alicyclic group.In some embodiments according to the present invention, R^*1And R^*2At least one of independently include electron attractive functional group, such as-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,- NCR^α,-SO₃H ,-COOH ,-CHO ,-F ,-Cl ,-Br ,-I ,-COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination, wherein often A R^αIt independently is hydrogen, C₁-C₂₀Alkyl etc..

In some embodiments according to the present invention, R^*1And R^*2It both independently include substituted or unsubstituted ring Pentadienyl, wherein R^*1And R^*2One of independently include following formula indicate substituted or unsubstituted cyclopentadienyl group:

Wherein C^*The connection carbon of the group is indicated, wherein each R¹⁸、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, C₁-C₄₀Hydrocarbon Base, the functional group comprising the element from periodic table of elements 13-17 race, in two or more R¹⁹、R²⁰、R²¹And R²²Solely On the spot it is joined together to form C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²,R¹³,R¹⁴、R¹⁵、 R¹⁶、R¹⁷、R¹⁹、R²⁰、R²¹And R²²Solely It is on the spot hydrogen, C₁-C₄₀Alkyl, the functional group comprising the element from periodic table of elements 13-17 race, R¹、R²、R³、R⁴、R⁵、 R⁶、R⁸、R⁹、R¹⁰、 R¹¹、R¹²,R¹³,R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、R²⁰、R²¹And R²²In two or more be independently connected C is formed together₄-C₆₂Cyclic annular or polycyclic ring structure or their combination；

Each R⁷And R¹⁸It independently is C₁-C₄₀Alkyl or function comprising the element from periodic table of elements 13-17 race Group；And

Y is divalent C₁-C₂₀Alkyl.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、 R¹⁹、R²⁰、R²³、R²⁴、R²⁵、R²⁶、 R²⁷、R²⁸、R²⁹And R³⁰It independently is hydrogen, C₁-C₄₀Alkyl, the functional group comprising the element from periodic table of elements 13-17 race, R¹、R²、R³、R⁴、R⁵、 R⁶、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、R²⁰、R²³、R²⁴、R²⁵、R²⁶、 R²⁷、R²⁸、R²⁹With R³⁰In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination；

Y is divalent C₁-C₂₀Alkyl.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、 R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、 R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸It independently is hydrogen, C₁-C₄₀Alkyl includes to come from periodic table of elements 13-17 race Element functional group, R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、 R²⁷、R²⁸、R²⁹、 R³⁰、R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸In two or more be separately attached to be formed together C₄-C₆₂It is cyclic annular Or polycyclic ring structure or their combination；

Y is divalent C₁-C₂₀Alkyl.

In a kind of embodiment according to the present invention, catalyst system includes the catalyst that activator and following formula indicate Compound:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Wherein C^*Indicate the connection carbon of the group；

Y is divalent C₁-C₂₀Alkyl.

In embodiments of the invention, method includes tying up to one or more alkene with caltalyst to be enough to generate It the temperature of polyolefin, pressure and is contacted under the time, which includes the catalyst compounds that activator and following formula indicate Object:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Wherein C^*Indicate the connection carbon of the group；

Y is divalent C₁-C₂₀Alkyl.

In some embodiments according to the present invention, R^*1And R^*2One of independently include substituted or unsubstituted C₄- C₂₀Aliphatic series or alicyclic group.In some embodiments according to the present invention, R^*1And R^*2At least one of independently include Electron attractive functional group, such as-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,-NCR^α,-SO₃H ,-COOH ,-CHO ,-F ,- Cl ,-Br ,-I ,-COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination, wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl Deng.In some embodiments according to the present invention, R^*1And R^*2The two independently includes substituted or unsubstituted cyclopentadiene Base, R^*1And R^*2One of them independently includes the cyclopentadienyl group that substituted or unsubstituted following formula indicates:

Detailed description of the invention

The height that Fig. 1 shows that the embodiment below according to embodiment of the present invention is prepared using Zr catalyst is entirely same Vertical structure is polyacrylic¹H H NMR spectroscopy.

Detailed description

In order to the present invention and appended claims purpose, the numbering plan of the periodic table of elements such as Chem.Eng.News, Used in 1985,63,27.Therefore, " group-4 metal " is the element of the 4th race of the periodic table of elements.

In all structures described in the present specification and claims, solid line indicates that key, arrow indicate that key can be Any position, and each dotted line represents the key with various degrees of valence state and various degrees of coordination.

Unless otherwise indicated, term " alkyl ", " hydrocarbyl group " and " hydrocarbyl group " are used interchangeably herein.For The purpose of present disclosure, alkyl are defined as in a suitable case (aromatic series or non-aromatic) can be straight chain, branch Chain or cricoid C₁-C₇₀Base or C₁-C₂₀Base or C₁-C₁₀Base or C₆-C₇₀Base or C₆-C₂₀Base or C₇-C₂₀Base；And including The alkyl replaced by the functional group of other alkyl and/or the element comprising one or more periodic table of elements 13-17 races.For The object here, part aromatic ring system include the ring bodies for capableing of disubstituted sp3 hydbridized carbon atoms containing at least one System.The example of part aromatic ring system includes tetrahydrofuran, indenes, fluorenes etc..The sp of compound rest part is connected to via it³It is miscellaneous Change carbon atom herein For the purpose of this paper and with Asterisk marks (C^*), such as in the following example:

In addition, two or more this alkyl can be formed together fused ring system, including the part containing heterocycle or Completely hydrogenated fused ring system.

For the purpose of this paper, fluorenyl or substituted fluorenyl are expressed from the next:

Wherein each R^1`To R^9`It independently is hydrogen, C₁-C₄₀Alkyl includes the member from periodic table of elements 13-17 race The functional group of element, R^1`-R^9`In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure, Or their combination.

Term " substituted " refer to hydrogen atom in foundation structure and/or carbon atom by alkyl and/or functional group, And/or hetero atom or containing heteroatomic group replace.Therefore, term alkyl includes containing heteroatomic group.In order to herein Purpose, hetero atom is defined as arbitrary atom in addition to carbon and hydrogen.For example, methyl cyclopentadiene (Cp) is by methyl The Cp group (it is basic structure) that (it is also known as methyl functional group) replaces, ethyl alcohol serves as reasons what-OH functional group replaced Ethyl (it is basic structure) and pyridine are the phenyl in the foundation structure of the phenyl ring replaced by nitrogen-atoms with carbon.

For the purpose of this paper, alkyl can independently selected from substituted or unsubstituted methyl, ethyl, vinyl, and with Under various isomers: propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ten Trialkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 20 One alkyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, two Octadecyl, nonacosyl, melissyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene Base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, 15 alkenyls, hexadecylene base, 17 alkenyls, ten Eight alkenyls, 19 alkenyls, icosa alkene base, two hendecene bases, docosene base, tricosene base, two tetradecene bases, 25 Alkenyl, cerotene base, 27 alkenyls, two octadecylene bases, 29 alkenyls, 30 alkenyls, propinyl, butynyl, pentyne Base, hexin base, heptynyl, octynyl, n-heptylacetylene base, decynyl, undecyne base, dodecyne base, tridecyne base, 14 alkynyls, 15 alkynyls, hexadecine base, 17 alkynyls, octadecyne base, 19 alkynyls, 20 alkynyls, two undecyne bases, two dodecyne bases, Two tridecyne bases, 24 alkynyls, 25 alkynyls, two hexadecine bases, 27 alkynyls, two octadecyne bases, 29 alkynes Base, He Sanshi alkynyl.Ranges described herein (such as C₁-C₁₀Alkyl), including the above-mentioned object with requirement carbon atom Class, for example, " C₁-C₁₀Alkyl " includes methyl, ethyl, vinyl and propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl The isomers of base and decyl.

For the purpose of this paper, hydrocarbyl group may also comprise the isomery of saturation, part unsaturation and aromatic cyclic structure Body, wherein above-described substitution type can additionally occur for group.

Term " aryl ", " aryl group ", and/or " aryl " refer to aromatic cyclic structure, it can be by defined herein Hydrocarbyl group and/or functional group replace.The example of aryl group includes: acenaphthenyl, acenaphthylene base, acridinyl, anthryl, benzanthracene Base, benzimidazolyl, benzo isoxazolyl, benzofluoranthrene base, benzofuranyl, benzo perylene base (benzoperylenyls), benzo pyrenyl, benzothiazolyl, aisaa benzothiophenyl, benzoxazolyl, benzyl, carbazyl, carboline It is base (carbolinyl), chrysenyl, cinnoline base, coronene base, cyclohexyl, cyclohexenyl group, methylcyclohexyl, dibenzo anthryl, glimmering Anthryl, fluorenyl, furyl, imidazole radicals, indazolyl, indeno pyrenyl, indyl, indolinyl, isobenzofuran-base, different Yin Diindyl base, isoquinolyl (isoquinolinyl), isoxazolyl, methylbenzyl, aminomethyl phenyl, naphthalene, oxazolyl, phenanthryl, benzene Base, purine radicals, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, quinazolyl, quinolonyl (quinolonyl), quinoxalinyl, thiazolyl, thiophenyl etc.

It should be understood that For the purpose of this paper, when group is listed, it indicates the group (types of radicals) and works as The foundation structure of all other group formed when the substitution of type defined above occurs for the group.Alkyl, the alkene listed Base and alkynyl include all isomers comprising cyclic isomers in a suitable case, for example, butyl includes normal-butyl, 2- methyl-propyl, 1- methyl-propyl, tert-butyl and cyclobutyl (and similar substituted cyclopropyl)；Amyl includes n-pentyl, Cyclopenta, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1- ethyl propyl and neopentyl (and similar substituted ring Butyl and cyclopropyl)；Cyclobutenyl includes 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- methyl-1-propylene base, 1- methyl -2- Acrylic, the E and Z-type of 2- methyl-1-propylene base and 2- methyl -2- acrylic (and cyclobutane base and cyclopropanyl).It is cyclic annular It includes the form of all isomers that compound, which has substituent group, for example, aminomethyl phenyl includes ortho-methyl phenyl, m- methylbenzene Base and p- aminomethyl phenyl；3,5-dimethylphenyl include 2,3- 3,5-dimethylphenyl, 2,4- 3,5-dimethylphenyls, 2,5- 3,5-dimethylphenyls, 2,6- diphenyl methyls, 3,4- 3,5-dimethylphenyls and 3,5- 3,5-dimethylphenyl.

Similarly, unless otherwise indicated, term " functional group ", " group " are also interchangeably used herein and " replaces Base ".For the purpose of this paper, functional group includes organic with inorganic group or comprising the periodic table of elements the 13rd, 14,15,16,17 The part of the element of race.Suitable functional group may include alkyl, for example, alkyl, alkenyl, aryl and/or halogen (Cl, Br, I, F), O, S, Se, Te, And/or wait, wherein eachIndependently be hydrogen or more than limited Fixed C₁-C₂₀Alkyl and wherein x are suitable integer to provide the part of electroneutral.Other examples of functional group include typical case Ground is referred to as amine, acid imide, amide, ether, alcohol (hydroxide), sulphion, sulfate radical, phosphonium ion, halogen ion, phosphonate radical, alkane Alcohol, ester, carboxylate radical, those of aldehyde etc..

For the purpose of this paper, the catalyst and/or activator of load refer in carrier or what is be connected to carrier urges Perhaps wherein the activator, the catalyst compounds or their combination are heavy for their combination for agent compound, activator Product is gasified with carrier, is keyed on carrier, is incorporated into carrier, adsorbed or be absorbed into carrier on carrier, absorption or suction It is received on carrier.

For the purpose of this paper, electron attractive functional group, which refers to, removes electricity from conjugated π system via resonating or incuding electrophilic Sub- density, for example, thus making the more electrophilicity atom of π system or functional group.It includes nitro that the example of electron group, which is inhaled, (-NO₂), quaternary amines (- NR₃ ⁺), three halogenated group (- CF₃,-CCl₃,-CBr₃,-CI₃), cyano group (- CN), isocyano group Group (R^αCN-)；Sulfonic group (- SO₃H), carboxylic acid (- COOH), ester (- COOR), aldehyde (- CHO) and/or ketone (- COR^α), or Their combination etc., wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl.

When mentioning two substituent groups herein and being joined together to form cyclic annular or polycyclic ring structure, replace when two When base only forms the covalent bond for being free of atom together, a substituent group is directly bridged to another substituent group, that is to say, that if They together comprise at least the bridge of an atom, then the substituent group is not directly connected.

For the purpose of this paper, huge functional group is defined with the molecule ruler more than or equal to isopropyl group part Very little functional group.Therefore, For the purpose of this paper, huge functional group includes substituted or unsubstituted with three or more The huge aliphatic group of carbon, the huge alicyclic group with three or more carbon, and/or with 5 or more carbon Bulky aromatic group group, each have the molecular dimension more than or equal to isopropyl group part.

For the purpose of this paper, " alkene (olefin) " is also referred to as " alkene (alkene) ", is comprising carbon and hydrogen and tool There are the straight chain, branch or cyclic compound of at least one double bond.For the purpose of this specification and its appended claims, when Polymer or copolymer are referred to as when including alkene, and the alkene for being present in this polymer or copolymer is the alkene of polymeric species Hydrocarbon.For example, when copolymer is described as having " ethylene " content of 35wt%-55wt%, it should be understood that in copolymer Link units derive from polymerization reaction in ethylene and the poidometer of the obtained unit based on the copolymer with 35wt%-55wt% exists.

For the purpose of this paper, " polymer " has two or more identical or different " chain link " units." homopolymerization Object " is the polymer with identical link units." copolymer " is with two or more respective different link units Polymer." trimer " is that there are three types of the polymer of respectively different link units for tool.The table of " difference " about link units Show that link units have at least one atom different each other or are different isomers.Therefore, copolymerization used herein The definition of object includes trimer etc..Oligomer is typically to have the polymer of low molecular weight, and such as less than 25,000g/mol Mn, or lower than the link units of 2,500g/mol or low number, such as 75 in a kind of embodiment according to the present invention A link units are less." ethene polymers " or " ethylene copolymer " is the list derived from ethylene comprising at least 50 moles % The polymer or copolymer of member, " acrylic polymers " or " propylene copolymer " are the list that propylene is derived from comprising at least 50 moles of % The polymer or copolymer of member, and so on.

For the purpose of present disclosure, term " alpha-olefin " includes C₂-C₂₂Alkene.The unrestricted example of alpha-olefin Attached bag includes ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene, 1- hendecene 1- Laurylene, 1- tridecylene, 1- tetradecene, ten pentaene of 1-, 1- hexadecylene, 17 alkene of 1-, 1- octadecylene, 19 alkene of 1-, 1- bis- Ten alkene, bis- hendecene of 1-, 1- docosene, 1- tricosene, bis- tetradecene of 1-, 1- pentacosa alkene, 1- cerotene, 1- bis- 17 alkene, bis- octadecylene of 1-, 29 alkene of 1-, 30 alkene of 1-, 4-methyl-1-pentene, 3- Methyl-1-pentene, 5- methyl-1- Nonene, 3,5,5- trimethyl -1- hexenes, vinyl cyclohexane and vinyl norbornene alkane.Cycloolefin and alkadienes are unrestricted The example of property includes cyclopropylene, cyclobutane, cyclopentene, cyclohexene, cycloheptene, cyclo-octene, cyclonoene, cyclodecene, norborneol Alkene, 4- methyinorbornene, 2- methyl cyclopentene, 4- methyl cyclopentene, vinyl cyclohexane, norbornadiene, two rings penta 2 Alkene, 5- ethylidene -2- norbornene, vinylcyclohexene, 5- vinyl -2- norbornene, 1,3- divinyl pentamethylene, 1,2- divinylcyclohexane, 1,3- divinylcyclohexane, Isosorbide-5-Nitrae-divinylcyclohexane, 1,5- divinyl cyclooctane, 1- allyl -4- vinyl cyclohexane, Isosorbide-5-Nitrae-diallyl hexamethylene, 1- allyl -5- vinylcyclooctane and 1,5- bis- Allyl cyclooctane.

Term " catalyst ", " catalyst compounds " and " transistion metal compound " is defined as referring in suitable item The compound of the polymerization of monomer to polymer can be caused under part.In explanation here, the catalyst can be described as urging Agent precursor, procatalyst compound or transistion metal compound, and these terms are interchangeably used.Catalyst compounds It can be with itself come using causing catalysis or cause with activator combination use catalysis.When catalyst compounds and work Agent combines come when causing catalysis, catalyst compounds are commonly known as procatalyst or catalyst precarsor." catalyst system " At least one catalyst compounds, at least one activator, optional conactivator) and optional carrier material group It closes, wherein the system can be by monomer polymerization at polymer.For the purpose of the present invention and appended claims, work as catalyst System is described as the group timesharing comprising neutral stable form, those of ordinary skill in the art would be well understood component from Sub- form is and monomer reaction is in the form of generating polymer.

" anion ligand " is the ligand for the negative electricity that one or more pairs of electronics are given metal ion by band." neutral donor is matched Body " is the ligand that one or more pairs of electronics are given to the neutral charge of metal ion.

Scavenger is to be typically added by removing impurity to promote the compound of polymerization.Some scavengers can also fill When activator and it can be referred to conactivator.It is not that the conactivator of scavenger can also be used together to form work with activator Property catalyst.In one embodiment of the invention, conactivator can be pre-mixed to form alkylation with catalyst compounds Catalyst compounds.

As used in this article, Mn is by as described herein¹The number-average molecular weight of H NMR measurement, Mw attach most importance to respectively Son amount and Mz are the z average molecular weight measured by gel permeation chromatography as described herein (GPC), and wt% is weight hundred Divide ratio, mol% is molar percentage.Alternatively, when GPC is inaccurate for low molecular weight species, for according to ASTM The kinematic viscosity of D445 (KV100) measurement is lower than the polymer of 10cSt at 100 DEG C, and Mw and Mn can pass through gas chromatography (GC) Measurement is 10cSt or higher for KV100, is measured by GPC.Molecular weight distribution (MWD) is defined as Mw divided by Mn.It removes It is non-separately to have annotation, all molecular weight units, for example, Mw, Mn, Mz g/mol.

Being right in this explanation can be used abbreviation below: Me is methyl, and Ph is phenyl, and Et is ethyl, and Pr is propyl, iPr For isopropyl, n-Pr is n-propyl, and Bu is butyl, and iso-butyl is isobutyl group, and sec-butyl is sec-butyl, and tert-butyl is tertiary fourth Base, n-butyl are normal-butyl, and pMe is p- methyl, and Bn is benzyl, and THF is tetrahydrofuran, and Mes is mesitylene methyl, also by Referred to as 1,3,5- trimethylbenzenes, Tol is toluene, and Flu is fluorenyl, and TMS is trimethyl silyl, and TIBAL is triisobutyl Aluminium, TNOAL are triisobutyl octyl aluminum, and MAO is methylaluminoxane and MOMO is methoxymethoxy (also referred to as methoxy Ylmethyl ether), N is nitrogen (including N¹、N²、N³And N⁴Respectively indicate single nitrogen-atoms) and O be oxygen.

For the purpose of this paper, RT is room temperature, unless otherwise indicated, is defined as 25 DEG C.So percentage is weight Percentage (wt%), unless otherwise indicated.

In the explanation of this paper, Salan catalyst may be described as catalyst precarsor, procatalyst compound, Salan catalyst compounds or transistion metal compound, and these terms are used interchangeably.

Catalyst compounds

In a kind of embodiment according to the present invention, catalyst includes being loaded by four tooth dianion Salan ligands The race of 3rd, 4,5 and/or 6 mono-substituted (for trivalent metal) or disubstituted (for tetravalent metal) compound, can be used for Olefin polymerization and/or alpha-olefin are to generate polyolefin and/or poly- (alpha-olefin).In a kind of embodiment according to the present invention, Catalyst compounds are expressed from the next:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Wherein C^*Indicate the connection carbon of the group；

Y is divalent C₁-C₂₀Alkyl.

In some embodiments according to the present invention, R^*1And R^*2At least one of independently include it is substituted or unsubstituted C₄-C₂₀Aliphatic series or alicyclic group.In some embodiments according to the present invention, R^*1And R^*2At least one of independently Including electron attractive functional group, such as-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,-SO₃H ,-COOH ,-CHO ,-F ,-Cl ,- Br ,-I ,-COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination etc., wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl.? In some embodiments according to the present invention, R^*1And R^*2The two independently includes substituted or unsubstituted cyclopentadienyl group, R^*1 And R^*2One of them independently includes the substituted or unsubstituted cyclopentadienyl group that following formula indicates:

Wherein C^*The connection carbon of the group is indicated, wherein each R¹⁸、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, C₁-C₄₀Hydrocarbon Base, the functional group comprising the element from periodic table of elements 13-17 race, R¹⁹、R²⁰、R²¹And R²²In two or more solely On the spot it is joined together to form C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Y is divalent C₁-C₂₀Alkyl.

In a kind of embodiment according to the present invention, R⁸And R⁹, R¹⁰And R¹¹, R¹⁹And R²⁰(when it is present) and R²¹ And R²²(when it is present) at least one set is separately attached to be formed together aromatics or part aromatic ring system in.

In a kind of embodiment according to the present invention, R⁸And R⁹, R¹⁰And R¹¹, R¹⁹And R²⁰(when it is present) and R²¹With R²²(when it is present) at least one set is separately attached to be formed together at least one hexa-atomic aromatic ring in.

In a kind of embodiment according to the present invention, R⁸And R⁹And/or R¹⁰And R¹¹It is separately attached to be formed together Indenyl or fluorenyl ring system, R¹⁹And R²⁰(when it is present) and/or R²¹And R²²(when it is present) it is separately attached to be formed together Indenyl or fluorenyl ring system or their combination.

In a kind of embodiment according to the present invention, each R⁷And R¹⁸It independently is methyl, ethyl, propyl, butyl, Amyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl and their isomers, preferably methyl, phenyl And/or tert-butyl.

In a kind of embodiment according to the present invention, Y is divalent C₁-C₂₀Alkyl, it includes such part, the portions Subpackage is contained in nitrogen-atoms N¹And N²Between connect or bridge joint 1-18 carbon atom linker skeleton.According to the present invention one In kind embodiment, which includes O, S, S (O), S (O)₂, Si (R^#)₂, P (R^#), N or N (R^#), wherein each R^#Independently For hydrogen or C₁-C₁₈Alkyl.In a kind of embodiment according to the present invention, Y is the-CH derived from propylene₂CH₂CH₂-。

In a kind of embodiment according to the present invention, Y is divalent C₁-C₁₂Aliphatic group, can for cyclic annular, branch or Straight chain.

In a kind of embodiment according to the present invention, Y is selected from methylene, ethyl, propyl, butyl, amyl, hexyl, pungent Base, nonyl, decyl, undecyl, dodecyl, phenyl and their isomers.

In a kind of embodiment according to the present invention, Y is ethylidene (- CH₂CH₂), 1,2- cyclohexylidene, 1,2- is sub- Phenyl or 2- benzal, that is, benzal bridge structure N¹-Y-N²It is expressed from the next:

Or

In a kind of embodiment according to the present invention, M Hf, Ti or Zr.

In a kind of embodiment according to the present invention, each X¹And X²(work as X²In the presence of) it independently is halogen or C₁-C₇ Alkyl.

In a kind of embodiment according to the present invention, each X¹And X²(work as X²In the presence of) independently be selected from 1- The alkyl of 20 carbon atoms, hydrogen ion, amino, with the alkoxy radical of 1-20 carbon atom, sulphur root, phosphorus root, halogen root, amine, Phosphine, ether and their combination.

In a kind of embodiment according to the present invention, each X¹And X²(work as X²In the presence of) it is benzyl.

In a kind of embodiment according to the present invention, each R¹、R²、R³、R⁴、R⁵、R⁶、 R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、 R¹⁴、R¹⁵、R¹⁶、R¹⁷(and R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, halogen or C when it is present)₁-C₃₀Alkyl.

In a kind of embodiment according to the present invention, each R¹、R²、R³、R⁴、R⁵、R⁶、 R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、 R¹⁴、R¹⁵、R¹⁶、R¹⁷(and R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, halogen or C when it is present)₁-C₁₀Alkyl.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Y is divalent C₁-C₂₀Alkyl.

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Y is divalent C₁-C₂₀Alkyl.

In a kind of embodiment according to the present invention, in above-mentioned catalyst compounds:

X¹And X²For benzyl；

R¹、R⁵、R⁷、R¹²、R¹⁶And R¹⁸For methyl；

R²、R³、R⁴、R⁶、R¹³,R¹⁴、R¹⁵、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、 R³⁰、R³¹、R³²、R³³、R³⁴、R³⁵、 R³⁶、R³⁷And R³⁸For hydrogen；And

Y is ethylidene (- CH₂CH₂), as following formula indicates:

Wherein M is Zr or Hf.

X¹And X²For benzyl；

R¹、R⁵、R¹²And R¹⁶For methyl；

R⁷And R¹⁸For benzyl；

Y is ethylidene (- CH₂CH₂), as following formula indicates:

Wherein M, N¹, N², X¹, X², O, each R¹To R¹⁷And R^*1And R^*2It is as defined above, and wherein each R³⁹And R⁴⁰ It independently is hydrogen, C₁-C₄₀Alkyl, the functional group comprising the element from periodic table of elements 13-17 race or R³⁹And R⁴⁰Even It is connected together to form C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.

Wherein M, N¹, N², X¹, X², O, each R¹To R¹⁷And R^*1And R^*2It is as defined above (that is, Y is substituted or unsubstituted 2- benzal or N¹-Y-N²For substituted or unsubstituted 2- aminobenzyl amine moieties).Therefore, in a kind of reality of the invention It applies in scheme, Salan ligand is the asymmetric substitution around metallic atom M.

Wherein M, N¹, N², X¹, X², O, R^*1And R^*2It is as defined above, wherein each R⁴¹、R⁴²、 R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷、 R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、R⁵³And R⁵⁴It independently is hydrogen, C₁-C₄₀Alkyl includes the member from periodic table of elements 13-17 race The functional group of element, R⁴¹、R⁴²、 R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷、R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、R⁵³And R⁵⁴In two or more It is separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.Therefore, according to the present invention In a kind of embodiment, N¹-Y-N²It, can be according to R for substituted or unsubstituted bipyrrolidine group part^*1And R^*2Composition and/ Or replaces and chirality is introduced into Salan ligand system.

In one embodiment of the present invention, method includes making one or more alkene and according to one or more realities The caltalyst for applying scheme ties up to temperature, pressure and the time contact for being enough to generate polyolefin.In embodiment of the present invention In, catalyst compounds are placed on carrier.

In one embodiment, the present invention includes by the side according to one or more embodiments disclosed herein The polyolefin that method obtains.In embodiments of the invention, it is that at least the ethylene of 500,000g/mol is poly- which, which includes Mw, Close object.In embodiments of the invention, which includes the acrylic polymers that isotacticity is at least 90%. In embodiments of the invention, the Mw of the polyolefin is at least 500,000g/mol.

Wherein each solid line indicates that covalent bond, each dotted line indicate that there is different degrees of valence state to match with different degrees of The key of position；

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, C₁-C₄₀Alkyl, comprising coming From the functional group of the element of periodic table of elements 13-17 race, in two or more R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、 R¹⁴、R¹⁵、R¹⁶And R¹⁷It is separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination；

Y is divalent C₁-C₂₀Alkyl；And

Wherein R^*1It independently is the substituted or unsubstituted cyclopentadienyl group of following formula expression:

Wherein C^*1Indicate the connection carbon of the group,

And wherein R^*2It independently is the substituted or unsubstituted cyclopentadienyl group of following formula expression:

Wherein C^*2The connection carbon of the group is indicated, wherein each group is independently via benzyl ring and cyclopentadienyl group Between single carbon-to-carbon be keyed to corresponding benzyl ring, wherein each R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹⁸、R¹⁹、R²⁰、R²¹And R²² It independently is hydrogen, C₁-C₄₀Alkyl, the functional group comprising the element from periodic table of elements 13-17 race, R⁸、R⁹、R¹⁰、R¹¹、 R¹⁹、R²⁰、R²¹And R²²In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure, or Their combination.

In one embodiment of the present invention, R⁷And R¹⁸It is each independently C₁-C₄₀Alkyl is all comprising coming from element The functional group of the element of phase Biao 13-17 race.

In one embodiment of the present invention, substituent R¹⁸To R²²Respectively each and R⁷To R¹¹It is identical.Of the invention In embodiment, substituent R¹⁸To R²²At least one of respectively with R⁷To R¹¹Dissmilarity, so that the Salan ligand system is opposite It is asymmetrical in metallic atom.

In embodiments of the invention, R^*1And R^*2At least one of independently include comprising with 3-20 carbon atom Aliphatic series or alicyclic group huge functional group.In one embodiment, R^*1And R^*2At least one of independently include Huge functional group, including isopropyl, substituted or unsubstituted cyclopentadienyl group, tert-butyl, cyclohexyl, hexose, furanose, gold Rigid alkyl and/or analog.

In embodiments of the invention, R^*1And R^*2At least one of independently include electron attractive functional group, including with Under it is one or more: nitro (- NO₂), three halogenation base (- CF₃,-CCl₃,-CBr₃,-CI₃), cyano (- CN), isocyano group (R^α CN-), sulfonic group (- SO₃H), carboxylic acid group (- COOH), aldehyde radical (- CHO), halogen (- F ,-Cl ,-Br ,-I), ester (- COOR^α), ketone (-COR^α) and/or ammonium (- NR^α ₃ ⁺), wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl.In embodiment of the present invention In, R^*1And R^*2At least one of independently include the huge functional group replaced by least one electron attractive functional group.

In a kind of embodiment according to the present invention, R^*1And R^*2At least one of independently be selected from comprising following formula appoint The substituted or unsubstituted group of one of meaning:

Wherein C^*For the connection carbon of the group, and each of various possible substituent group independently is hydrogen, C₁-C₄₀Hydrocarbon Base, functional group or their combination comprising the element from periodic table of elements 13-17 race.According to the present invention one In kind embodiment, each R^*1And R^*2It independently include identical group.

In embodiments of the invention, the R in one of above-mentioned any catalyst compounds¹And R¹²In the presence of it is independent The C that ground is selected from methyl and position halogen is held to replace₁-C₄Alkyl, for example, trifluoromethyl or 2,2,2- trifluoroethyls.For example, in this hair Bright wherein R¹For methyl and R¹²It is in the embodiment of 2,2,2- trifluoroethyls, catalyst compounds are expressed from the next:

Wherein M, N¹, N², X¹, X², O, R²To R⁶, R¹³To R¹⁷, R^*1And R^*2As defined above.

In another embodiment of the invention, catalyst compounds are expressed from the next:

Wherein R¹And R¹²It is all 2,2,2- trifluoroethyls, and wherein M, N¹, N², X¹, X², O, R²To R⁶, R¹³To R¹⁷, R^*1 And R^*2As defined above.

The method for preparing catalyst compounds

In a kind of embodiment according to the present invention, symmetrical transistion metal compound can pass through two kinds of overall synthesis roads It is prepared by line.

React A:

React B:

React C:

Parent Salan ligand can prepare (reaction A) from parent phenol by a step Mannich reaction, or if use Corresponding salicylide prepares (reaction B) by two step imines condensations/alkylation step.Then by being risen with four metal aryls Beginning raw material, such as tetrabenzyl reaction generate the (reaction of final complex by the ligand transformations at metal dibenzyl based catalyst precursors C)。

In a kind of embodiment according to the present invention, asymmetric transistion metal compound can pass through gradually synthetic route Preparation.Then parent Salan ligand can use NaBH by corresponding salicylide and diamine reactant₄Also original preparation.Then not Symmetrical ligand can be formed by the HBr elimination reaction (reacting D) of the phenol substituted with bromo- alkyl-.Then the ligand can lead to It crosses to react with tetrabenzyl metal starting material and be converted to metal diaikyl (such as dibenzyl metal catalysts precursors), generate most Whole complex (reaction E).

React D:

React E:

Activator

Term " co-catalyst " and " activator " be employed interchangeably describe activator and be defined as can by will in Property catalyst compounds are converted into the catalyst compounds cation of catalytic activity to activate above-described any catalyst Close any compound of object.Unrestricted activator, it may for example comprise aikyiaiurnirsoxan beta, alkyl aluminum, (it can be with for Ionizing activators It is neutral or ion), and routine-type co-catalyst.Activator may include aluminium alkoxide compound, modified alumina alkanisation Close object, and separation reactivity, σ-bonding metal ligand, so that metal complex cationsization and offer charge balance Noncoordinating or Weakly coordinating anions ionizing anionic precursors compounds.

In one embodiment, alumoxane activator is used as the activator in carbon monoxide-olefin polymeric.Aikyiaiurnirsoxan beta is usually Contain-Al (R¹)-O- subunit oligomeric compound, wherein R¹For alkyl.The example of aikyiaiurnirsoxan beta includes methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.Alkylaluminoxane and modified alumina Alkane is suitable for catalyst activator, especially when catalyst precursor compounds include separable ligand (it is alkyl, halogen from Son, alkanol or amide).Also the mixture of different aikyiaiurnirsoxan beta and modified aikyiaiurnirsoxan beta can be used.In a kind of embodiment In, visual clear methylaluminoxane can be used.Muddy or gel aikyiaiurnirsoxan beta be may filter that generate clear solution or can Clear aikyiaiurnirsoxan beta is poured out from muddy solution.Available aikyiaiurnirsoxan beta is that modified methylaluminoxane (MMAO) is described in U.S. Patent number 5,041,584 is commercially available from Akzo Chemicals, Inc. with trade (brand) name 3A type modified methylaluminoxane.

In a kind of embodiment according to the present invention, (wherein TMA is trimethyl aluminium to the activator that activator is poor TMA Abbreviation).Inventor is advantageously discovered that facilitating preparation using the alkylaluminoxane of poor TMA has compared with the high allyl end of the chain Polymer.Commercially available aikyiaiurnirsoxan beta, such as methylaluminoxane (MAO) and isobutyl aluminium alkoxide often include that some remaining startings are former Material is used as impurity.For example, a kind of common method for preparing MAO is the hydrolysis of trimethyl aluminium (TMA).However, such hydrolysis Remaining TMA is often left in MAO, this may adversely affect polymerization.Any removing known in the art can be used The method of TMA.In a kind of embodiment according to the present invention, for example, in order to generate the activator of poor TMA, it can be by aikyiaiurnirsoxan beta Solution of (such as methylaluminoxane) such as 30wt% in toluene is diluted in toluene, and for example, by pseudocuminol with The combination of solid filtering removes alkyl aluminum (such as TMA in MAO) from solution.In a kind of reality according to the present invention It applies in scheme, the activator of poor TMA includes about 14 wt% trimethyl aluminium of about 1wt%-, or is lower than 13wt% trimethyl aluminium, or Person is lower than 12wt% trimethyl aluminium, is perhaps perhaps lower than 5wt% trimethyl aluminium or 0wt% lower than 10wt% trimethyl aluminium Trimethyl aluminium, and/or, it is greater than 0wt% trimethyl aluminium, or be greater than 1wt% trimethyl aluminium.

When activator is aikyiaiurnirsoxan beta (modified or unmodified), in a kind of embodiment according to the present invention, activation The Al/M of about 5000 times of molar excess of the maximum of agent typically catalyst compounds (every metal catalytic site).In basis In a kind of embodiment of the invention, according to the minimum activation relative to catalyst compounds of the concentration mensuration of transition metal M Agent is typically about 1 moles, of aluminum per mole of titanium metal or less every mol of transition-metal M.In a kind of embodiment according to the present invention, work as work When agent includes aikyiaiurnirsoxan beta, aikyiaiurnirsoxan beta exists with the ratio of every 1 moles, of aluminum per mole of titanium metal of mole catalyst immunomodulator compounds or more.According to this In a kind of embodiment of invention, minimum activator is typically 1:1 molar ratio relative to the molar ratio of catalyst compounds. Other example ranges of Al:M include 1:1-500:1 perhaps 1:1-200:1 perhaps 1:1-100:1 or 1:1-50:1.

In a kind of embodiment according to the present invention, little or no aikyiaiurnirsoxan beta (being lower than 0.001wt%) is for this In polymerization described in text.In a kind of embodiment according to the present invention, aikyiaiurnirsoxan beta exists with 0.00 mole of %, or Aikyiaiurnirsoxan beta is lower than 500:1 with aluminium and catalyst compounds transition metal, is perhaps perhaps lower than 100:1 or low lower than 300:1 Exist in the molar ratio of 1:1.

Scavenger or conactivator

In a kind of embodiment according to the present invention, which can further comprise scavenger and/or total work Agent.Suitable alkyl aluminum or organo-aluminum compound, can be used as scavenger or conactivator, including, for example, trimethyl aluminium, Triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc..Other oxyphie species, such as diethyl zinc can be used. In a kind of embodiment according to the present invention, scavenger and/or conactivator are lower than 14wt% by the catalyst system, or Person 0.1-10wt% or 0.5-7wt% exist.

Carrier

In a kind of embodiment according to the present invention, catalyst system may include inert carrier.According to the present invention In a kind of embodiment, carrier includes porous carrier, such as talcum and/or inorganic oxide.Other suitable carriers include Zeolite, clay, organic clay or any other organic or inorganic carrier etc. or their mixture.

In a kind of embodiment according to the present invention, carrier is the inorganic oxide of levigate form.For urging for this paper The suitable inorganic oxide material of agent system includes the 2nd, 4,13 and 14 family metal oxide, such as silica, oxygen Change aluminium and their mixture.It can individually or and other inorganic oxides for using jointly of silica and/or aluminium oxide Group including magnesia, titanium oxide, zirconium oxide, montmorillonite, phyllosilicate and/or analog and these carrier materials It closes, including silica-chromium, silica-alumina, silica-titania etc..In a kind of implementation according to the present invention In scheme, carrier material includes Al₂O₃、ZrO₂、SiO₂、 SiO₂/Al₂O₃And their combination.Other suitable carriers include mill Thin functionalised polyolefin, such as levigate polyethylene.

In a kind of embodiment according to the present invention, it is about 700 m of about 10- that carrier, which can have range,²The surface area of/g, The average particle size particle size or range that the pore volume and range that range is about 0.1- about 4.0cc/g are about 500 μm of about 5- are about 50- About 500m²The pore volume and about 200 μm of about 10- of average particle size particle size of the carrier surface area of/g, about 0.5- about 3.5cc/g.? In a kind of embodiment according to the present invention, the range of most of carrier surface area is about 100- about 400m²/ g, pore volume are About 0.8- about 3.0cc/g and average particle size particle size are about 100 μm of about 5-.In a kind of embodiment according to the present invention, carrier The range of average cell size beOr 50- is aboutOr 75- is aboutAccording to the present invention A kind of embodiment in, carrier be high surface area, it is amorphous have greater than or equal to about 300m²The surface area of/gm, greatly In or equal to about 1.65cm³The silica of the pore volume of/gm.Suitable silica with trade name Davison 952 or Davison 955 is commercially available by the Davison Chemical Division of W.R.Grace and Company.According to this hair In a kind of bright embodiment, carrier may include Davison 948.

In a kind of embodiment according to the present invention, carrier should be substantially dry, that is, substantially free of absorption Water.At about 100 DEG C-about 1000 DEG C, or the temperature of at least about 400 DEG C or 500 DEG C or 600 DEG C can be by heating or calcining Carry out the drying of carrier.When carrier is silica, at least 200 DEG C, or about 200 DEG C-about 850 DEG C are heated to, or at least 600 DEG C, for about 1 minute-about 100 hours, or about 12 hours-about 72 hours, or about 24 hours-about 60 hours.According to this Disclosure, in a kind of embodiment according to the present invention, the carrier of calcining must have at least some reactive hydroxyls (OH) group is to generate load type catalyst system.

In a kind of embodiment according to the present invention, by the carrier of calcining and at least one include at least one catalysis The contact of the polymerization catalyst of immunomodulator compounds and activator.In a kind of embodiment according to the present invention, there are reactive surfaces The carrier of group (typically hydroxyl), slurried in the nonpolar solvent and slurry generated and catalyst compounds and work The solution of agent contacts.In a kind of embodiment according to the present invention, the slurry of carrier contacts about 0.5 with activator first - about 24 hours hour, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours periods.Then, by catalyst compounds The solution of object is contacted with carrier/activator of isolation.It is in situ to generate support type in a kind of embodiment according to the present invention Catalyst system.In alternate embodiments, the slurry of carrier contacted first with catalyst compounds about 0.5 hour-about 24 hours, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours time.Then, by supported catalyst immunomodulator compounds Slurry contacted with activator solution.

In a kind of embodiment according to the present invention, by catalyst, the mixture of activator and carrier is heated to about 0 DEG C-about 70 DEG C, or to about 23 DEG C-about 60 DEG C, or to room temperature.Time of contact is typically about 0.5 hour-about 24 hours, or about 2 hours-about 16 hours, or about 4 hours-about 8 hours.

Suitable nonpolar solvent is all reactants of this paper in the material wherein used, that is, activator and catalyst Compound is at least partially soluble and it is liquid at the reaction temperatures.Suitable nonpolar solvent includes alkane, such as different Pentane, hexane, normal heptane, octane, nonane and decane, but can also include cycloalkane using many other materials, such as Hexamethylene, aromatic compound, such as benzene, toluene and ethylbenzene.

In a kind of embodiment according to the present invention, activator, catalyst compounds or their combination are to pass through It contacts activator, catalyst compounds or both of the above with carrier and loads, to form the activator of load, negative The catalyst of load perhaps their combination wherein activator, catalyst compounds or their combination be deposited on carrier, Gasified by carrier, be keyed on carrier, mixing in carrier, adsorb or be absorbed into carrier or adsorb or be absorbed into carrier On.

In a kind of embodiment according to the present invention, catalyst compounds, activator and/or catalysis disclosed herein Agent system can be contacted with one or more carrier materials or carrying body.For example, in a kind of embodiment according to the present invention, Activator is contacted with carrier to form the activator of load, wherein activator be deposited in carrier or carrying body, with carrier or load Carrier contact is gasified by carrier or carrying body, is keyed on carrier, mixes in carrier or carrying body, adsorbs or be absorbed into load In body or carrying body or adsorbs or be absorbed into carrier or carrying body.

In a kind of embodiment according to the present invention, " equivalent is can be used in catalyst, activator or their combination Dipping " load, wherein contacted comprising the solution of activator, catalyst compounds or their combination with carrier, wherein solution Amount be carrier material absorptive capacity about 95- about 100%.

In a kind of embodiment according to the present invention, carrier material is chemically treated and/or is dehydrated, then with catalysis Immunomodulator compounds, activator and/or catalyst system combine.In a kind of embodiment according to the present invention, carrier material can have There are many horizontal dehydration, such as can be by realizing carrier material in about 200 DEG C-about 1000 DEG C dryings of temperature range.? Water reactive compounds, such as silane and organo-aluminum compound can be used chemically to be dehydrated these carriers.

In a kind of embodiment according to the present invention, the silica of dehydration can be with organo-aluminium or aluminium alkoxide compound Contact.In a kind of embodiment according to the present invention, when using organo-aluminum compound, activator is due to such as trimethyl Aluminium is formed in situ in carrier material with reacting for water.

In a kind of embodiment according to the present invention, carrier substrate and Lewis acidic activator containing lewis base Reaction, forms the carrier of bonded lewis acid compound.The Lewis base hydroxyl groups group of silica is as wherein generation It is keyed to metal/quasi-metal oxides example of the method for carrier.These embodiments are described in such as United States Patent (USP) In No.6,147,173.

Other embodiments of supported activator are described in United States Patent (USP) No.5, and in 427,991, which describe derive from The non-coordinating anion of the load of three perfluorophenyl boron；United States Patent (USP) No.5,643,847, discuss the 13rd race's Lewis acid Close object and metal oxide, such as silica reacts, and illustrate three perfluorophenyl boron and silanol (silicon Hydroxyl group) reaction, generate can make transition metal organometallic type catalyst compounds protonate binding anion, Form the catalytic activity cation by the binding anion back balance.

In a kind of embodiment according to the present invention, the activator of load is formed in the following manner: in stirring The solution of activator and suitable solvent is prepared in the controlled container of temperature and pressure, then load is added in the temperature at 0 DEG C -100 DEG C Body material contacts carrier with activator solution at most 24 hours, then removes solvent using the combination of heat and pressure to produce The powder of raw flowing.Temperature can be with range at 40-120 DEG C, and pressure is 34.5kPa-138kPa (5psia-20 psia).It can be with It assists removing solvent using inert gas purge.Other order of addition can be used, such as make carrier material appropriate molten Pulp in agent, then adds activator.

In a kind of embodiment according to the present invention, activator exists relative to the weight percentage ranges of carrier material The weight percent of about 10 weight percent-about 70, in other embodiments, range is in the weight of about 20 weight percent-about 60 Percentage, in other embodiments, range is in the weight percent of about 30 weight percent-about 50, in yet other embodiments In, range is in the weight percent of about 30 weight percent-about 40.

The catalyst system that can be used for the load of embodiment disclosed herein includes such caltalyst loaded System, they are formed in the following manner: making carrier material, activator and catalyst compounds in various ways in a variety of conditions Under catalyst loader device outer contacting.

In a kind of embodiment according to the present invention, catalyst compounds, activator and carrier can be used as mineral slurry oil Material feeds polymer reactor as the slurry in liquid diluent.Solid concentration in mineral oil or liquid diluent can be Range is in about 30 weight percent of about 3- in some embodiments；And about 25 weight percent of about 10- in other embodiments Than.

In a kind of embodiment according to the present invention, catalyst compounds used in the present invention, activator and/or Carrier also discriminably or is together spray-dried, and is then injected into reactor.Spray-dried catalyst, which can be used as powder or solid, to be made With, or can be placed in diluent and be added in reactor as slurry.In a kind of embodiment according to the present invention, it will carry Body is in conjunction with one or more activators and is spray-dried the activator to form load.In a kind of embodiment party according to the present invention In case, by fumed silica in conjunction with methylaluminoxane, then spray drying forms the methylaluminoxane of load, and carrier can In conjunction with aikyiaiurnirsoxan beta, spray drying is subsequently placed in the slurry that formation can be used according to the disclosure in mineral oil.According to this hair In a kind of bright embodiment, above-mentioned catalyst compounds can be with one or more carrier materials and/or one or more activation Agent combines, and is spray-dried, then in conjunction with slurry diluent.

In a kind of embodiment according to the present invention, by catalyst compounds and/or activator and carrier material, example If particulate filler material combines, then it is spray-dried, free flowing powder can be formed.Spray drying can be known in the art Any mode.In a kind of embodiment according to the present invention, catalyst can be spray-dried in the following manner: by catalyst Compound and activator are placed in solution, such as need to make catalyst compounds and activator fuel oil, add filler material, such as Then silica and/or fumed silica force solution to reach nozzle in high pressure.Solution can be sprayed on surface or It is sprayed in a manner of drying drop in air.The method generallyd use is to disperse silica in toluene, is being activated It stirs in agent solution, is then stirred in catalyst compound solution.Slurry concentration can be about 5-8wt%.Such preparation Slurry can be used as under gentle agitation or manually oscillation, and there are longest 30 minutes, to keep being used as suspension before spray drying. In a kind of embodiment according to the present invention, the group of dry material becomes about 40-50wt% activator (for example, alumina Alkane), 50-60SiO₂About 2wt% catalyst compounds.

In a kind of embodiment according to the present invention, final step axis can be by two or more catalyst compounds Object is added together with desired ratio.In another embodiment, more complicated process is possible, such as addition first Reaction time t as defined in catalyst compounds to activator/filler mixture, then adds the second catalyst compound solution, Another defined time x is mixed, later by mixture co-spray.Finally, another additive, for example, about 1- of 10vol% Hexene can reside in activator/filler mixture, then add the first catalyst compounds.

In a kind of embodiment according to the present invention, binder is added in mixture.These can be used as improvement Grain form (even if size distribution narrow), the porosity for reducing particle and the means for reducing aikyiaiurnirsoxan beta amount are added, and play The effect of " binder ".

In a kind of embodiment according to the present invention, it is anti-that polymerization is fed using spray-dried granules as mineral oil slurry It answers in device.Solid concentration in oil is about 10-30wt% or 15-25wt%.In a kind of embodiment according to the present invention In, the size of spray-dried granules can be for below about 10 microns-about 100 microns, in contrast, the catalyst of conventional load It is about 50 microns.In a kind of embodiment according to the present invention, the average particle size of carrier is 1-50 microns or 10-40 Micron.

In a kind of embodiment according to the present invention, catalytic component is used for according to the carbon monoxide-olefin polymeric of the disclosure In slurry and/or in catalyst component solution.For purposes of this disclosure, slurry is defined as the suspension of solid in a liquid, Middle solid may or may not be porous.Catalytic component slurry is merged to form catalyst combination with catalyst component solution Object is then introduced into polymer reactor.In a kind of embodiment according to the present invention, catalytic component slurry includes Activator and carrier or the activator of load.In a kind of embodiment according to the present invention, slurry is in addition to activator and load It also include catalyst compounds except body and/or the activator of load.In a kind of embodiment according to the present invention, slurry In catalyst compounds be load.In a kind of embodiment according to the present invention, slurry includes one or more activation Agent and carrier and/or the activator and/or one or more catalyst compounds of load.For example, slurry may include two kinds or More kinds of activators (such as the aikyiaiurnirsoxan beta of load and modified aikyiaiurnirsoxan beta) and catalyst compounds or slurry may include bearing The activator of load and more than one catalyst compounds.In a kind of embodiment according to the present invention, slurry includes load Activator and two kinds of catalyst compounds.

In a kind of embodiment according to the present invention, slurry includes the activator and two different catalyst of load Compound, they respectively or can be added in combination slurry.In a kind of embodiment according to the present invention, loaded aluminium will be contained The slurry of oxygen alkane is contacted with catalyst compounds, is reacted them, is contacted slurry with another catalyst compounds.? In another embodiment, the slurry containing loaded aikyiaiurnirsoxan beta is contacted simultaneously with two kinds of catalyst compounds, and make it React.The gold in metal and catalyst compounds in a kind of embodiment according to the present invention, in slurry in activator The molar ratio of category is 1000:1-0.5:1 perhaps 300:1-1:1 or 150:1-1:1.

Polymerization

In a kind of embodiment according to the present invention, polymerization includes making monomer (such as ethylene and propylene), and appoint The comonomer of choosing and the above-mentioned caltalyst comprising activator and at least one catalyst compounds tie up to and are enough to generate polyene It the temperature of hydrocarbon, pressure and is contacted under the time.In a kind of embodiment according to the present invention, catalyst compounds and activator It can merge in any order, and can the merging before being contacted with monomer.In a kind of embodiment according to the present invention, catalysis Immunomodulator compounds and/or activator merge after contacting with monomer.

In a kind of embodiment according to the present invention, two or more different catalyst compounds are present in this It invents in the catalyst system used.In a kind of embodiment according to the present invention, two or more different catalyst Compound is contained therein the reaction zone that one or more methods as described herein carry out.Transition metal compound is based on when two kinds When the catalyst of object is used in a reactor as mixed catalyst system, by two kinds of transistion metal compounds selections To make them two be compatible.Compatible catalyst is with the similar dynamics terminated and be inserted into monomer and comonomer And/or it will not those of destructive interaction catalyst each other.For the purpose of this paper, term " incompatible catalyst " Refer to the catalyst for meeting one or more of:

1) activity of at least one of catalyst is reduced more than those of 50% catalyst in the presence of together；

2) polymer is generated under the conditions of same reaction makes the molecular weight of one of polymer be other polymer molecules Those of twice of amount or more catalyst；And

3) it is more than about 30% in the same terms comonomer incorporation or reactive proportional difference.Those skilled in the art are The simple screening method known, such as pass through¹H or¹³C NMR, being determined for which catalyst transistion metal compound is phase Hold.In a kind of embodiment according to the present invention, catalyst system is that catalyst compounds use identical activator. In a kind of embodiment according to the present invention, two or more different activators can be applied in combination, such as non-match Complex anion activator and aikyiaiurnirsoxan beta.If one or more catalyst compounds contain be not hydrogen ion or alkyl X¹Or X² Ligand contacts aikyiaiurnirsoxan beta with catalyst compounds, it is non-then to add this then in a kind of embodiment according to the present invention Non-coordinating anion activator.

In a kind of embodiment according to the present invention, when having used two kinds of transistion metal compound (procatalysts), They can be used in any proportion.In a kind of embodiment according to the present invention, First Transition metallic compound (A) and the The molar ratio of two transistion metal compounds (B) falls into range (A:B) 1:1000-1000:1 perhaps 1:100-500:1 or 1: 10-200:1 perhaps 1:1-100:1 perhaps 1:1-75:1 or 5:1-50:1.Selected special ratios depend on selected Specific procatalyst, activation method and desired final product.In a kind of embodiment according to the present invention, work as use When two kinds of procatalysts, when both with the activation of identical activator, the total mole number based on procatalyst, available mole Percentage be 10:90-0.1:99 perhaps 25:75-99:1 perhaps 50:50-99.5:0.5 perhaps 50:50-99:1 or 75:25-99:1 or 90:10-99:1.

The available monomer of the present invention includes substituted or unsubstituted C₂-C₄₀Alhpa olefin or C₂-C₂₀Alhpa olefin or C₂-C₁₂α Alkene or ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, hendecene, laurylene are different with theirs Structure body.In one embodiment of the invention, monomer includes propylene and optional comonomer, which includes second Alkene or C₄-C₄₀Alkene or C₄-C₂₀Alkene or C₆-C₁₂One of alkene is a variety of.C₄-C₄₀Olefinic monomer can be straight chain, Branch is cricoid.C₄-C₄₀Cycloolefin can be nervous or non-anxiety, monocycle or polycyclic, and optionally include miscellaneous Atom and/or one or more functional groups.In embodiments, monomer includes ethylene or ethylene and comonomer includes one kind Or a variety of C₃-C₄₀Alkene or C₄-C₂₀Alkene or C₆-C₁₂Alkene.C₃-C₄₀Olefinic monomer can be straight chain, branch, or ring-type 's.C₃-C₄₀Cycloolefin can be nervous or non-anxiety, monocycle or polycyclic, and optionally include hetero atom and/or one Kind or a variety of functional groups.

Illustrative C₂-C₄₀Olefinic monomer and optional comonomer include ethylene, propylene, butylene, amylene, hexene, heptan Alkene, octene, nonene, decene, hendecene, laurylene, norbornene, norbornadiene, bicyclopentadiene, cyclopentene, cycloheptyl Alkene, cyclo-octene, cyclo-octadiene, cyclododecene, 7- oxanorbornene, 7- oxanorbornadiene, the substituted of them spread out Biology and their isomers or hexene, heptene, octene, nonene, decene, laurylene, cyclo-octene, 1,5- cyclo-octadiene, 1- Hydroxyl -4- cyclo-octene, 1- acetoxyl group -4- cyclo-octene, 5- methyl cyclopentene, cyclopentene, bicyclopentadiene, norbornene, drop Borneol diene and their own homologue and derivative or norbornene, norbornadiene and bicyclopentadiene.

In a kind of embodiment according to the present invention, total weight of one or more diene based on the composition It is present in at most 10 weight % or 0.00001-1.0 weight % or 0.002-0.5 weight % or 0.003-0.2 weight % In the polymer generated herein.In a kind of embodiment according to the present invention, by 500ppm or less or 400ppm or more Few or 300 ppm or less diene are added to polymerization.In a kind of embodiment according to the present invention, will at least 50ppm, Or the diene of 100ppm or more or 150ppm or more is added to polymerization.

Diolefinic monomer for use in the present invention includes any hydrocarbon structure or C₄-C₃₀, there are at least two unsaturated bonds , wherein at least two unsaturated bond easily passes through Stereoselective or non-cubic catalyst of selecting is incorporated to polymer.In basis In a kind of embodiment of the invention, diolefinic monomer be can be selected from α, ω-diene monomers (i.e. two-vinyl monomers).It is excellent Selection of land, diolefinic monomer is two-vinyl monomer of straight chain, more or to contain those of 4-30 carbon atom.The example of diene Attached bag includes butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon two Alkene, oleatridecadiene, 14 carbon diene, pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon Diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, 25 Carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, 1,6- heptan Diene, 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, 1,10- ten one carbon diene, 1,11- ten two carbon diene, 1,12- Oleatridecadiene, 1,13- ten four carbon diene and low molecular weight polybutadiene (Mw is lower than 1000g/mol).Cyclic diene includes Cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene or contain bicyclopentadiene Have advanced ring is with or without the alkadienes of substituent group in each ring position.

In one embodiment of the invention, wherein butylene is comonomer, and butylene source can be to include various butylene The mixed butene stream of isomers.It is expected that by polymerization and preferably consumes 1- butene monomers.This mixed butylene material The use of stream will provide economic benefit, due to these mixing stream typical from process for refining waste streams, for example, C₄ Raffinate stream, and therefore can dramatically it is cheaper than pure 1- butylene.

Polymerization can be carried out according to present disclosure in such a way that this field is any of.This field can be used Known any suspension, homogeneously, ontology, solution, slurry or gas phase polymerization process.These methods can with interval, semi-batch, Or continuous mode carries out.Homogeneous polymerization method and slurry process be here it is applicable, wherein homogeneous polymerization method is defined It is soluble method in reaction medium for the wherein at least product of 90wt%.Ontology homogeneous process be here it is applicable, Wherein bulk process is defined as the method that wherein all monomer concentrations being fed into reactor are 70 volume % or more. In a kind of embodiment according to the present invention, solvent or diluent are not present or are added into reaction medium, (in addition to few Amount is used as the carrier of catalyst system or other additives, or the amount typically found together with monomer；For example, in propylene Propane).In a kind of embodiment according to the present invention, method is slurry process.Term as used herein " slurry polymerization Method ", which refers to, wherein uses the polymerization that loaded catalyst and monomer polymerize on supported catalyst particle.At least The polymer product derived from loaded catalyst of 95wt% is used as solid particle in granular form (insoluble in diluent).

Suitable diluent/solvent for polymerization includes noncoordinating, inert fluid.Example includes straight chain and branch Hydrocarbon, such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and their mixture； Cyclic annular and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and their mixture, such as It can (Isopar^TM) commercially available；Full halogenated hydrocarbon, such as perfluorinated C_4-10Alkane, chlorobenzene and aromatic radical and alkyl-substituted fragrance Compounds of group, such as benzene, toluene, mesitylene and dimethylbenzene.Suitable solvent also includes that may act as monomer or comonomer Liquefied olefines, the liquefied olefines include ethylene, propylene, 1- butylene, 1- hexene, 1- amylene, 3- Methyl-1-pentene, 4- first Base -1- amylene, 1- octene, 1- decene and their mixture.In a kind of embodiment according to the present invention, aliphatic Hydrocarbon solvent is used as solvent, such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and Their mixture；Cyclic annular and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and they Mixture.In a kind of embodiment according to the present invention, solvent is not aromatic compound or aromatic compound base In the poidometer of the solvent to be present in solvent less than 1wt% or less than 0.5 wt% or less than 0.0wt%.

In a kind of embodiment according to the present invention, it is based on for the monomer of polymerization and the input concentration of comonomer The total volume meter of the feed steam is 60vol% solvent or less or 40 vol% or less or 20vol% or less.Institute State polymerization can also be to carry out in bulk process.

Polymerization can be carried out in the case where being suitable for obtaining desired polyvinyl any temperature and/or pressure.Suitable temperature And/or it is about 0 DEG C-about 300 DEG C that pressure, which includes range, or about 20 DEG C-about 200 DEG C, or about 35 DEG C-about 150 DEG C, or about 50 DEG C- About 150 DEG C, or about 40 DEG C-about 120 DEG C, or about 45 DEG C-about 80 DEG C of temperature；Be about 0.35MPa- about 10MPa in range, Or about 0.45MPa- about 6MPa, or the pressure of about 0.5MPa- about 4MPa.

In a kind of embodiment according to the present invention, the progress time of reaction is about 0.1 minute-about 24 hours, or extremely More 16 hours or range are about 5-250 minutes, or about 10-120 minutes.

In a kind of embodiment according to the present invention, hydrogen at 0.007-345 kPa (0.001-50psig), or It is present in polymer reactor under the partial pressure of 0.07-172kPa (0.01-25psig) or 0.7-70 kPa (0.1-10psig) In.

In a kind of embodiment according to the present invention, the activity of catalyst is at least 50 g/mmol/ hours or 500g/ Mmol/ hours or more or 5000g/mmol/hr or more or 50,000g/mmol/hr or more.In alternative embodiment party In formula, the conversion ratio of olefinic monomer is at least 10%, the monomer weight or 20% based on polymer yield and entrance reaction zone Or more or 30% or more or 50% or more or 80% or more.

In a kind of embodiment according to the present invention, polymerizing condition includes below one or more: 1) 0-300 DEG C The temperature of (or 25-150 DEG C or 40-120 DEG C or 45-80 DEG C)；2) atmospheric pressure -10MPa (or 0.35-10MPa or 0.45- 6MPa or 0.5-4MPa) pressure；3) aliphatic hydrocarbon solvent (such as iso-butane, butane, pentane, isopentane, hexane, dissident Alkane, heptane, octane, dodecane and their mixture；Cyclic annular and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, methyl cyclohexane Alkane, methylcycloheptane and their mixture；Or in which poidometer of the aromatic compound based on the solvent is to be less than 1wt% or less than 0.5wt% or 0wt% are present in solvent) presence；4) the wherein caltalyst used in polymerization It is the aikyiaiurnirsoxan beta comprising being less than 0.5mol% or 0mol% or aikyiaiurnirsoxan beta to be less than 500:1 or less than 300:1, or less than The aluminium of 100:1 or less than 1:1 and the molar ratio of transition metal exist；5) it is aggregated in a reaction zone and carries out；6) catalyst The yield of compound is at least 80,000g/mmol/hr (or at least 150,000g/mmol/hr, or at least 200,000 g/ Mmol/hr, or at least 250,000g/mmol/hr, or at least 300,000g/mmol/hr)；7) scavenger (such as trialkylaluminium Compound) there is no (for example, with zero mol% presence) or scavenger to be less than 100:1 or less than 50:1 or less than 15:1, Or less than 10:1；Or the scavenger and transition metal equal to or less than about 8:1 molar ratio exist, optionally hydrogen with 0.007-345kPa (0.001-50psig) (or 0.07-172kPa (0.01-25psig) or 0.7-70kPa (0.1- Partial pressure 10psig)) is present in polymer reactor.

In a kind of embodiment according to the present invention, the catalyst system used in polymerization includes not more than one kind Catalyst compounds." reaction zone " (also referred to as " polymeric area ") is the container polymerizeing, such as batch reactor.When When using multiple reactors with the structure of serial or parallel connection, each reactor is considered as separated polymeric area.For in interval Multi-step polymerization in formula reactor and flow reactor, each polymerization stage are considered as separated polymeric area.In basis In a kind of embodiment of the invention, it is aggregated in a reaction zone and carries out.

Polyolefin product

Present disclosure further relates to the composition of matter produced by method described herein.

In a kind of embodiment according to the present invention, method described herein produces Noblen or propylene is total Polymers, such as propylene-ethylene with the Mw/Mn for being greater than 1-4 (or be greater than 1-3) and/or propylene-alpha-olefin (or C₃-C₂₀) altogether Polymers (such as butene-hexene copolymer or propylene-octene Copolymer).

Similarly, method of the present invention produces olefin polymer or polyethylene and polypropylene homopolymer and copolymerization Object.In a kind of embodiment according to the present invention, the polymer produced herein is the homopolymer of ethylene or propylene, is ethylene Or one or more C with 0-25 moles of % (or 0.5-20 moles of % or 1-15 moles of % or 3-10 moles of %)₃-C₂₀ Olefin comonomer (or C₃-C₁₂Alpha-olefin or propylene, butylene, hexene, octene, decene, laurylene or propylene, butylene, oneself Alkene, octene) copolymer, or for propylene or there is 0-25 moles of % (or 0.5-20 moles of % or 1-15 moles of % or 3-10 Mole %) one or more C₂Or C₄-C₂₀Olefin comonomer (or ethylene or C₄-C₁₂Alpha-olefin or ethylene, butylene, oneself Alkene, octene, decene, laurylene or ethylene, butylene, hexene, octene) copolymer.

In a kind of embodiment according to the present invention, which is ethylene and comonomer is hexene or 1-15 It rubs % hexene or 1-10 rubs % hexene.

In a kind of embodiment according to the present invention, the Mw of polymer prepared by the present invention is at least 500,000g/ Mol, or at least 800,000g/mol, or at least 1,000,000 g/mol, or at least 1,200,000g/mol, or At least 1,500,000g/mol and/or Mw/Mn be greater than 1-40 perhaps 1.2-20 perhaps 1.3-10 perhaps 1.4-5 or 1.5-4 1.5-3.

In a kind of embodiment according to the present invention, the polymer produced herein has by gel permeation chromatography (GPC) The unimodal or multimodal molecular weight distribution of measurement." unimodal " refers to that GPC trace has a peak or inflection point." multimodal " refers to GPC trace Measurer has at least two peaks or inflection point.Inflection point is the sign modification of the wherein second dervative of curve (for example, from negative to positive or instead ) point.

In a kind of embodiment according to the present invention, the polyolefin using catalyst preparation of the invention can be complete same Vertical structure, height isotaxy, syndiotaxy or height syndiotactic propylene polymer.As used in this article, " isotaxy " It is defined as with basis¹³At least the 10% of C-NMR analysis derives from the isotaxy five-tuple of the methyl group of propylene, preferably has There is at least 40% isotaxy five-tuple.As used in this article, " height isotaxy " is defined as with basis¹³C- At least 60% isotaxy five-tuple of NMR analysis.In desired embodiment, polyolefin (preferably polypropylene) has extremely Few 85% isotacticity, perhaps at least 90% isotacticity or at least 95% isotaxy rule Whole degree.As used in this article, " syndiotaxy " is defined as with basis¹³At least 10% syndiotaxy of C-NMR analysis Five-tuple, preferably at least 40%.

In a kind of embodiment according to the present invention, polymer can be straight chain characteristic, can by elution fractionation come Determine, wherein the CDBI of non-linear polymer be lower than 45%, and straight linear polyethylene type refer to CDBI be greater than 50% poly- second Alkene, the CDBI are measured as described in WO93/03093 (US5206075).In a kind of embodiment according to the present invention, this The composition Distribution Breadth Index (CDBI) for inventing the polymer of preparation is 50% or higher perhaps 60% or higher or 70% Or it is higher.CDBI is the measurement of composition distribution of the monomer in polymer chain, and passes through the PCT of announcement on 2 18th, 1993 Announce that WO 93/03093 is especially in the 7th and 8 columns and Wild et al. is in J.Poly.Sci., Poly.Phys.Ed., Vol.20, p.441 it is equal to ignore weight when determining CDBI for (1982) and United States Patent (USP) No.5, the measurement of process described in 008,204 Molecular weight (Mw) is lower than the fraction of 15,000g/mol.

Mw/Mn is 4.5 or lower polymer may include the long chain branching of the level of signifiance.Long chain branching is interpreted as end position Unsaturated polymer chain combines that (the specific end position encountered by single site catalysts is not in a manner of being similar to monomer and combine Saturated reaction mechanism is formed) arrive other polymer chains result.Therefore it is believed that branch is the structure of straight chain and can be¹³C There is no peak that can belong to the horizontal of the long chain branch in NMR spectra to exist.In a kind of embodiment according to the present invention, Polymer according to disclosure preparation includes the long chain branching of significant quantity, is defined as basis¹³Having for C NMR spectra measurement is every The ratio of the long chain branching of 1000 carbon atom at least seven carbon is greater than 0.5.In a kind of embodiment according to the present invention, root According to¹³Every 1000 carbon atoms of C NMR spectra measurement have the long chain branching ratio of the branch of at least seven carbon greater than 1, or Greater than 1.5, or it is greater than 2.

It include the ethylene of significant quantity according to polymer prepared by the disclosure in a kind of embodiment according to the present invention Base sealing end, the ratio for being defined as per molecule vinyl groups are greater than or equal to 0.2.In a kind of embodiment according to the present invention In, when according to J.American Chemical Soc., description or its equivalent in 114,1992, pp.1025-1032 are surveyed Periodically, according to the polymer of the disclosure include per molecule vinyl groups ratio be greater than or equal to 0.5 perhaps 0.7 or 0.8 perhaps 0.9 or 0.95.

In a kind of embodiment according to the present invention, the acrylic polymers using catalyst preparation of the invention includes At least 50% vinyl or the unsaturated end of the chain.In embodiments of the invention, at least 90%, or at least 95%, Huo Zhezhi Few 99% ethylidene end of the chain.

The present invention relates to the ethene polymers with both ethenyl blocking and long chain branching, and the ethene polymers is in root According in a kind of embodiment of the invention pass through The methods disclosed herein and use catalyst preparation disclosed herein.In basis In a kind of embodiment of the invention, method described herein prepares Alathon or ethylene copolymer, such as ethylene-α- Alkene or C₃-C₂₀Copolymer, such as ethylene-propylene copolymer, ethylene-hexene co-polymers or ethylene-octene copolymer, It includes

A) at least 50% allyl chain ends, or at least 60%, 70%, 80%, 90%, 95%, 98% or 99%； And/or

B) pass through¹The Mn that H NMR is measured is at least 200g/mol or 250 g/mol-100,000g/mol, such as or Person 200g/mol-75,000g/mol, such as 200g/mol-60,000g/mol or 300g/mol-60,000g/ Mol or 750g/mol-30,000g/mol；And/or

C) branch or 1.0 or more of at least 0.5 of every 1000 carbon atoms of atom with 7 or more carbon, Perhaps 1.25 or more perhaps 1.5 or more perhaps 1.75 or more perhaps 2.0 or more or 0.0- 5.0 perhaps 1.0-4.0 or 1.0-3.0；And/or

D) Tm is 100 DEG C or perhaps 110 DEG C or higher or 120 DEG C or higher higher；And/or

E) methyl chain end (the also referred herein as saturation end of the chain) and the ratio of allyl chain ends are 1:1-5:1 or 1:1- 4:1 or 1:1-3:1；And/or

F) pass through¹H NMR measurement, at least 50wt%, perhaps at least 60wt% perhaps at least 70wt% or at least 80wt%, perhaps the polymer of at least 90wt% or at least 95wt%, can be Alathon or copolymer, have every 1 vinyl of molecule or each chain；And/or it there is no presence or the polymer comprising less equal than about 0.01wt% diene；And/or

G) polymer includes at least 50mol% ethylene, perhaps at least 60mol% or at least 70mol%, Huo Zhezhi Few 75mol%, perhaps at least 80mol% perhaps at least 85mol% perhaps at least 90mol% or at least 95mol%, or The substantially ethylene of 100mol%；And/or

H) Mw/Mn be greater than 1-4, or be greater than 1-3.

In a kind of embodiment according to the present invention, polymer prepared by the present invention has the aluminium lower than 1400ppm, Perhaps perhaps perhaps lower than 500ppm or it is lower than 100ppm lower than 1000ppm lower than 1200ppm, passes through ICPES (inductance Coupled plasma optical emission spectrum) measurement, it is described in Encyclopedia of Materials Characterization J.W.Olesik " Inductively Coupled Plasma-Optical Emission Spectroscopy ", C.R.Brundle, C.A.Evans, Jr. and S.Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp.633-644, the document is used to determine herein the purpose of the amount of element in material；And/or according to the present invention A kind of embodiment in, the polymer have lower than 1400ppm the group 4 transition metal of the 3rd, 4,5 or 6 or the 4th race's mistake Cross metal perhaps Ti, Zr and/or Hf perhaps lower than 1200ppm perhaps lower than 1000ppm perhaps lower than 500ppm or Lower than 100ppm, measured by ICPES as described above.

In a kind of embodiment according to the present invention, had according to the ethene polymers of the disclosure lower than 1400ppm's Hafnium perhaps perhaps perhaps lower than 500ppm or is lower than 100ppmas lower than 1000ppm lower than 1200ppm, passes through ICPES Measurement.

In a kind of embodiment according to the present invention, had according to the ethene polymers of the disclosure lower than 1400ppm's Zirconium perhaps perhaps perhaps lower than 500ppm or is lower than 100ppm lower than 1000ppm lower than 1200ppm, is surveyed by ICPES It is fixed.

In a kind of embodiment according to the present invention, polymer prepared by the present invention can be ethene polymers, close Degree is, greater than 0.95g/cc, is perhaps greater than 0.955g/cc or is greater than 0.96g/cc.

In a kind of embodiment according to the present invention, polyvinyl branch index (g' prepared by the present invention_vis) It is 0.9 or less perhaps 0.85 or less or 0.80 or less, wherein g'_visIt is measured as follows.

For the present invention and its purpose of appended claims, Mw, Mz, carbon atom number g value and g '_visIt is to be arranged using high temperature Resistance chromatography (coming from Waters Corporation or Polymer Laboratories) passes through gel permeation chromatography (GPC) it measures, according to analyte and required analysis with there are three on-line checking device, differential refractive index detectors (DRI), light scattering (LS) detector and viscosimeter.Experimental detail (including detector correction) description exists: T.Sun, P.Brant, R.R.Chance and W.W.Graess ley, Macromolecules, the 19th phase of volume 34, the 6812-6820 pages, (2001) With bibliography therein.Use-B LS the column or its equivalence of three Polymer Laboratories PL gel 10mm mixing Object.Nominal flow velocity is 0.5cm³/ min and nominal volume injected are 300 μ L.Various transmission lines, column and differential refractometer (DRI detector) is placed in the stove for being maintained at 145 DEG C.Solvent for the experiment is the 6g by that will be used as antioxidant Butylated hydroxy-methylbenzene be dissolved in 1,2,4 trichloro-benzenes of Aldrich SILVER REAGENT (TCB) of 4L come what is prepared.Then the TCB Mixture then passes through 0.1 μm of Teflon filter filtering by 0.7 μm of glass pre-filter filtering.Then the TCB into It is de-gassed before entering exclusion chromatography with on-line degassing machine.Polymer solution is such as preparation of getting off: dry polymer is placed in In glass container, the TCB of desired amount is added, then by the mixture 160 DEG C and continuously stir it is lower heating about 2 hours.All Amount be to be measured by gravimetric analysis.The TCB density of polymer concentration for being indicated with mass/volume unit is in room Temperature is 1.463g/mL and is 1.324g/mL at 145 DEG C.Implantation concentration is 0.75-2.0mg/mL, and lower concentration is used In higher molecular species.Before running each sample, DRI detector and syringe are purified.Then the flow velocity in equipment Increase to 0.5mL/min, and stablizes DRI 8-9 hours before injecting the first sample.LS is swashed before Run sample Light device is opened 1-1.5 hours.Concentration c in chromatogram at each point is the DRI signal I subtracted by baseline_DRI, under use The equation in face calculates:

C=K_DRII_DRI/(dn/dc)

Wherein K_DRIIt is the constant measured by correcting DRI, (dn/dc) is the index increment of system.At 145 DEG C and The refractive index n=1.500 of TCB when λ=690nm.In order to the present invention and its appended claims purpose, acrylic polymers (dn/dc)=0.104, butene polymers is 0.098, and others are 0.1.Join used in the SEC method of this specification Number unit makes concentration with g/cm³It indicates, is indicated with g/mol, inherent viscosity is indicated with dL/g.

LS detector is Wyatt Technology High temperature mini-DAWN or its equivalent.In the every of chromatogram Molecular weight M at a point be by analysis LS output, using for static light scattering Zimm model (M.B.Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971) come what is measured:

Wherein, Δ R (θ) is the excessive Rayleigh intensity measured by scatteringangleθ, and c is measured by DRI analysis Polymer concentration, A₂It is second virial coefficient [for the purposes of the present invention, the A of acrylic polymers₂=0.0006, butylene is poly- Closing object is 0.0015, and others are 0.001], (dn/dc)=0.104 of acrylic polymers, butene polymers are 0.098, Others are that 0.1, P (θ) is form factor for monodispersity random coil, K_oIt is the optical constant of system:

Wherein N_AIt is Avogadro constant number, (dn/dc) is the index increment of system.At 145 DEG C and λ=690nm TCB refractive index n=1.500.

(it has with four capillarys of Wheatstone bridge configuration arrangement high temperature Viscotek Corporation viscosimeter Pipe and two pressure sensors) or its equivalent be used to measure specific viscosity.One sensor measurement along detector stagnation pressure Drop, another sensor is located between the two sides of the bridge and measure differences in pressure.Flow through the specific viscosity η of the solution of viscosimeter_sIt is It is calculated from their output.Inherent viscosity [η] at each point of chromatogram is calculated by following equation:

η_s=c [η]+0.3 (c [η])²

Wherein c is concentration and is measured by DRI output.

Branch index g'_visIt is the output using SEC-DRI-LS-VIS method such as calculating of getting off.The average spy of sample Property viscosity [η]_avgIt is calculate by the following formula:

Wherein summation is on the chromatography section i between limit of integration.Branch index g'_visIts is defined as:

Wherein for the present invention and its purpose of the attached claims, α=0.695 of linear tetrafluoroethylene polymer and k= 0.000579, α=0.695 and k of α=0.705 of linear propylene polymer and k=0.000262 and linear butylene polymer =0.000181.M_vIt is viscosity-average molecular weight,

It is based on the molecular weight measured by LS analysis.

" g " is also referred to as " g value ", is defined as Rg² _pm/Rg² _ls, wherein Rg_pmFor the radius of gyration for polymerizeing macromolecular, Rg² _ls For the radius of gyration of straight chain reference substance, and Rg_ls=K_sM^0.58, wherein K_sFor the coefficient of power law, (straight linear polyethylene is 0.023, linear polypropylene is 0.0171, the 0.0145 of straight chain polybutene) and M is above-mentioned molecular weight, Rg_pm=K_TM^αs。 α_sFor the size factor for polymerizeing macromolecular, K_TFor the coefficient of the power law of polymerization macromolecular.Referring to Macromolecules, There is in 2001,34,6812-6820 to selection the straight chain reference substance of the molecular weight and co-monomer content, and determine K The guidance of coefficient and alpha index.

In order to the present invention and its appended claims purpose, Mn (¹H NMR) it is measured according to following NMR method.¹H NMR Data use Varian spectrum under room temperature or 120 DEG C (for the purpose of claim, should use 120 DEG C) in 5mm probe Instrument is with 250MHz, 400MHz or 500MHz¹H frequency (for the purpose of claim, uses the proton frequency of 400MHz Rate) it collects.Using 45 DEG C of maximum pulse, 8 seconds and signal averaging 120 is instantaneous records data between pulse.By light Spectrum signal integral, and the quantity of the unsaturated type of every 1000 carbon passes through with different group numbers multiplied by 1000 and by result It is calculated divided by total carbon number.Mn passes through unsaturated species sum and calculates divided by 14,000, unit g/mol.

Crystallization temperature (T_c), melt temperature (or fusing point, T_m), glass transition temperature (T_g) and fusing heat (H_f) commercially available Instrument (for example, TA instrument 2920DSC) on using differential scanning calorimetry (DSC) measure.Typically, at room temperature by 6- The molded polymeric object or plasticized polymer of 10mg is sealed in aluminium dish and is loaded into instrument.In the 10 DEG C/min rate of heat addition, pass through by Sample is heated to above at least 30 DEG C of melt temperature (being typically 220 DEG C for polypropylene) and obtains data.Sample is in the temperature The lower holding of degree at least 5 minutes to eliminate thermal history.Then under the cooling rate of 20 DEG C/min, sample is cooled to from melting At least 50 DEG C (being typically -100 DEG C for polypropylene) lower than crystallization temperature.Sample is kept at least 5 minutes at such a temperature, And other melting data (second of heating) finally is obtained to heat in 10 DEG C/min.It is analyzed and is absorbed heat according to standard step Melting transition (being heated for the first time with second) and exothermic crystallization transformation.Unless otherwise indicated, the melt temperature (Tm) of report is Peak value melt temperature from second of heating.For showing the polymer at multiple peaks, melt temperature be defined as from The peak value melt temperature of the relevant fusing track of maximum caloric receptivity thermal response (rather than at peak that maximum temperature occurs).Equally Ground, crystallization temperature are defined as relevant from the maximum caloric receptivity thermal response of crystallization (rather than at peak that maximum temperature occurs) Crystallize the peak crystallization temperature of track.

Area under DSC curve is used to determine the heat of transformation (the hot H of fusing when melting_f, or crystallization heat H when crystallization_c), It can be used to calculate crystallinity (also referred to as percent crystallinity).Percent crystallinity (X%) is calculated using following formula: [bent Area (being indicated with J/g) under line/H ° (being indicated with J/g)] * 100, the wherein perfection of the H ° of homopolymer for major monomeric compoent The ideal fusing heat of crystallization.These H ° numerical value are to derive from Polymer Handbook, fourth edition, by John Wiley And Sons is published, and New York 1999, difference is, the numerical value of 290J/g is used for H ° (polyethylene), the numerical value of 140J/g H ° (polypropylene) is used for for the numerical value of H ° (polybutene) and 207J/g.

It (in addition to sample is cooled to -100 DEG C, keeps then being heated to 10 DEG C/min for 5 minutes using the above DSC step Except 200 DEG C) measurement melting heat (Hm).Measurement Hm is melted in first time, rather than second melts.Hm sample must be in room Warm aging at least 48 hours and elimination thermal history should not be heated.

By the ethylene contents in ASTM D 5017-96 or its equivalent measurement ethylene copolymer, in addition to the smallest noise Than should be except 10,000:1.Propylene content in propylene copolymer uses DiMartino and Kelchermans, J.Appl.Polym.Sci.56, the approach of the following methods 1 in 1781 (1995) determines, and uses the Polymer of Zhang45, the peak distribution of the higher alkene comonomer in 2651 (2004).

Blend

In a kind of embodiment according to the present invention, before forming film, mechanograph or other products, it will give birth to herein The polymer (or polyethylene or polypropylene) of production is in conjunction with one or more other polymer.Other available polymer packets Include polyethylene, isotactic polypropylene, height isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene, and/or fourth The random copolymer of alkene, and/or hexene, polybutene, ethylene vinyl acetate copolymer, LDPE, LLDPE, HDPE, ethylene propylene E pioic acid methyl ester copolymer, acrylic copolymer, polymethyl methacrylate any other can be gathered by high-pressure free radical method The polymer of conjunction, polyvinyl chloride, PB Polybutene-1, isotactic polybutene, ABS resin, EP rubbers (EPR), vulcanization EPR, EPDM, block copolymer, styrene block copolymer, polyamide, polycarbonate, PET resin, the polyethylene of crosslinking, ethylene Ethenol copolymer (EVOH), aromatic monomer polymer for example polystyrene, polyester, polyacetals, polyvinylidene fluoride, Polyethylene glycol, and/or polyisobutene.

In a kind of embodiment according to the present invention, polymer (or polyethylene or polypropylene) is based on the blend In polymer poidometer, with 10-99wt% or 20-95wt%, or at least 30-90wt%, or at least 40-90wt%, Or at least 50-90wt%, or at least 60-90wt%, or at least 70-90wt% is present in above-mentioned blend.

It can be by will be more than polymer of the present invention and one or more polymer (as described above) mixture manufacturing The blend is connected in series to prepare reactor blend, or by identical reactor by reactor The middle many kinds of substance that polymer is generated using more than one catalyst.Polymer can mix together before by injection extruder It closes or can mix in an extruder.

Blend can be used conventional device and method and be formed, such as by doing the individual component of blending and then existing Melting mixing in mixing machine, or by the mixed component in mixing machine together, for example, Banbury mixer, Haake mixing Machine, Brabender mixer or single or double screw extruder may include that the compounding in the direct downstream for polymerization is squeezed Machine and side wall extruder stream out may include the powder or particle in the loading hopper blending resin of film extruder.Additionally, Additive may include in the blend, in one or more components in the blend, and/or forming the product from blend, Such as film, as desired.This additive is well known in the art, and may include, for example: filler；Antioxidant (for example, by Phenol, such as IRGANOX 1010 or IRGANOX 1076 are hindered, Ciba-Geigy is purchased from)；Phosphorous acid salt is (for example, purchase From the IRGAFOS 168 of Ciba-Geigy)；Anti-sticking (anti-cling) additive；Tackifier, such as polybutene, terpenes tree Rouge, aliphatic and aromatic hydrocarbon resin, alkali metal and tristerin, and the rosin of hydrogenation；Ultra-violet stabilizer；It is hot steady Determine agent；Anticaking agent；Release agent；Antistatic agent；Pigment；Colorant；Dyestuff；Wax；Silica；Filler；Talcum etc..

Film

In a kind of embodiment according to the present invention, any polymer above-mentioned, such as polypropylene above-mentioned or it is total Mixed object, can be used for various terminals purposes application.Using including, for example, single or multiple layer inflation, extrusion, and/or shrink film.This A little films can be formed by any number of known extrusion or co-extrusion technology, such as blow molding vacuolar membrane processing technology, wherein institute Stating composition can be extruded in molten condition by cyclic annular mouth mold, then be expanded to form the melt being oriented either uniaxially or biaxially, It is cooled to the film of tubulose, blow molding later, then can axially cut and be unfolded to form flat film.Film can be then By disorientation, uniaxial orientation or biaxial orientation to identical or different degree.Film one or more layers can be with laterally and/ Or longitudinal direction is orientated to identical or different degree.Biaxial orientation may be implemented using typical cold drawing or hot-drawn method. Using tenter apparatus or double bubble process and biaxial orientation may be implemented and can be before or after individual course is aggregated.Example Such as, polyethylene layer can be extruded coating or be laminated on the polypropylene layer of orientation or polyethylene and polypropylene can be total to together Extruded shape film forming, is then orientated.Similarly, what the polypropylene of orientation can be in turn laminated on the polyethylene of orientation or be orientated is poly- Ethylene can be coated on polypropylene, and then optionally combination even can be further orientated.Typically, film is at most The ratio of 15 or 5-7 is orientated at longitudinal direction (MD), and with the ratio of at most 15 or 7-9 at transverse direction (TD).However, according to the present invention A kind of embodiment in film with identical degree the direction MD and TD be orientated.

The thickness variable of film, depending on required application；However, the film with a thickness of 1-50 μm is usually suitable.Envelope Film needed for dress is usually 10-50 μ m-thick.The thickness of sealant is typically 0.2-50 μm.The inner and outer surfaces of film can be with There are sealant or sealant that can be merely present in inner or outer surface.

In a kind of embodiment according to the present invention, one or more layers can by sided corona treatment, electron beam irradiation, γ radiation, flame treatment or microwave modification.In a kind of embodiment according to the present invention, pass through sided corona treatment modified surface One or two layers in layer.

Moulding article

Composition as described herein can also be used to prepare moulding article with any molding methods, including but not limited to, note It is moulded into type, gas assistant injection molding, extrusion and blow molding, injection-blow molding molding, injection stretch blow molding, compression molding, rotation Molding, foaming, thermoforming, sheet material squeezes out and section bar extrusion.Moulding process is that those of ordinary skill in the art are known.

Moreover, composition as described herein can form desired terminal by any suitable way known in the art Purposes product.Thermoforming is vacuum formed, blow molding, rotational forming, solidifying be moulded into type, transfer molding, wet-process coating or press Molding, cast molding, cold forming matched-die molding, injection molding, spraying technique, profile coextrusion or their combination are typical The method that ground uses.

Thermoforming is the method for making at least one flexible sheet plastic form desired shape.It typically, will be of the invention The extruded film (and any other layer or material) of the composition is placed in transmission frame to be held up during heating.It will pass Defeated frame is introduced in baking oven, before shaping pre-add hotting mask.Once heated film, transmission frame is backed into molding tool. Then, film is evacuated on molding tool to hold it in position appropriate and close molding tool by vacuum.The work Tool is remained turned-off with cooling film and then the tool is opened.Then, molding laminated product is taken out from the tool. Once the layer of material reaches hot-forming temperature, typically 140 DEG C -185 DEG C or higher, can be auxiliary by vacuum, positive air pressure, plug (plug-assisted) vacuum forming or these combination and version is helped to realize thermoforming.The bubble of pre-stretching is used Foam step especially improves the dispersion of material on big component.

Blow molding is the suitable molding mode of another kind for composition of the present invention comprising injection-blow molding Molding, multi-layer blow molding, extrusion and blow molding and stretch blow-molded, especially suitable for pair substantially close off or empty As for example, air accumulator and other fluid containers.The more details of blow molding are described in, for example, Concise Encyclopedia of Polymer Science and Engineering 90-92(Jacqueline I.Kroschwitz, ed., John Wiley&Sons 1990).

Likewise it is possible to make molten polymer form and be solidified into moulding article by the way that molten polymer to be injected into The mold of desired geometry and thickness manufactures moulding article.It can be squeezed by squeezing out substantially flat profile from punch die Out on chill roll, or by rolling manufacture thin slice.Thin slice is typically considered to have 254 μm -2540 μm (10 millimeter -100 Millimeter) thickness, but any given thin slice can be significantly thicker.

Non-woven fabrics and fiber

Above-described polyolefin composition can also be with any adhesive-bonded fabric and fibre manufacture (including but not limited to, Meltblown method, spun-bond process, film aperture (film aperturing) and staple card) it is used to prepare nonwoven of the present invention Fabric and fiber.Also continuous single fiber technique can be used.Or use spunbond process.Spunbond process is this field week Know.Usually it includes squeezing out fiber by spinning head.Then, these fibers are stretched using high-speed air and are layered on endless belt On.Then, pressure roller is normally used for heating net and is bonded to one another fiber, but other technologies also can be used, such as ultrasound Bonding and adhesive bonding.

Embodiment

Therefore, this disclosure relates to following embodiments:

E1. following formula indicate catalyst compounds:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Wherein C^*Indicate the connection carbon of the group；

Y is divalent C₁-C₂₀Alkyl.

E2. according to the catalyst compounds of embodiment E1, wherein each R^*1And R^*2It independently include replacing or not taking The cyclopentadienyl group and R in generation^*1And R^*2One of them independently includes the substituted or unsubstituted cyclopentadiene that following formula indicates Base:

Wherein each R¹⁸、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, C₁-C₄₀Alkyl, comprising from the periodic table of elements the The functional group of the element of 13-17 race, R¹⁹、R²⁰、R²¹And R²²In two or more be separately attached to be formed together C₄-C₆₂ Cyclic annular or polycyclic ring structure；Or their combination.

E3. according to the catalyst compounds of embodiment E1, wherein R^*1And R^*2At least one of independently include replace Or unsubstituted C₄-C₂₀Aliphatic series or alicyclic group.

E4. according to catalyst compounds one of any in embodiment E1 to E3, wherein R^*1And R^*2At least one of solely It on the spot include electron attractive functional group comprising-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,-SO₃H ,-COOH ,-CHO ,- F ,-Cl ,-Br ,-I ,-COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination, wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkane Base.

E5. according to catalyst compounds one of any in embodiment E1 to E4, wherein at least one of R^*1And R^*2 It independently include the hexa-atomic aromatic ring of a.

E6. according to catalyst compounds one of any in embodiment E1 to E5, wherein R⁸And R⁹, R¹⁰And R¹¹, R¹⁹And R²⁰(when it is present) and R²¹And R²²(when it is present) at least one set is separately attached to be formed together at least one in A hexa-atomic aromatic ring.

E7. according to catalyst compounds one of any in embodiment E1 to E6, wherein R⁸And R⁹And/or R¹⁰And R¹¹It is separately attached to be formed together indenyl ring system or fluorenyl ring system；

Wherein R¹⁹And R²⁰(when it is present) and/or R²¹And R²²(when it is present) it is separately attached to be formed together Indenyl ring system or fluorenyl ring system or their combination.

E8. according to catalyst compounds one of any in embodiment E1 to E7, wherein each R⁷And R¹⁸(work as presence When), it independently is C₁-C₁₂Aliphatic group or phenyl.

E9. according to catalyst compounds one of any in embodiment E1 to E8, wherein Y is cyclic annular, branch or straight chain Divalent C₁-C₁₂Alkyl.

E10. according to catalyst compounds one of any in embodiment E1 to E9, wherein Y is selected from methylene, ethylene, Propylene, butylidene, pentylidene, hexylidene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, sub- hexamethylene Base, phenylene and benzal.

E11. according to catalyst compounds one of any in embodiment E1 to E10, wherein Y be ethylidene (- CH₂CH₂), 1,3- propylidene (- CH=CHCH₂), 1,2- cyclohexylidene, 1,2- phenylene or 2- benzal.

E12. according to catalyst compounds one of any in embodiment E1 to E11, wherein M is Hf, Ti or Zr.

E13. according to catalyst compounds one of any in embodiment E1 to E12, wherein each X¹And X²Independently For halogen or C₁-C₇Alkyl.

E14. according to catalyst compounds one of any in embodiment E1 to E13, wherein each X¹And X²For benzyl.

E15. according to catalyst compounds one of any in embodiment E1 to E14, wherein each R¹、R²、R³、R⁴、 R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、 R¹⁷、R¹⁹、R²⁰、R²¹And R²²(when it is present) hydrogen, halogen independently are Or C₁-C₃₀Alkyl.

E16. according to catalyst compounds one of any in embodiment E1 to E15, wherein each R¹、R²、R³、R⁴、 R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、 R¹⁷、R¹⁹、R²⁰、R²¹And R²²(when it is present) hydrogen, halogen independently are Or C₁-C₁₀Alkyl.

E17. according to catalyst compounds one of any in embodiment E1 to E16, wherein R¹And R¹²Independently selected from The C that methyl and end position halogen replace₁-C₄Alkyl.

E18. according to catalyst compounds one of any in embodiment E1 to E17, wherein R¹And R¹²Independently selected from The C that methyl and end position halogen replace₁-C₄Alkyl, preferably haloform or 2,2,2- tri- halogen ethane, more preferable fluoroform or 2, 2,2- trifluoroethane.

E19. according to catalyst compounds one of any in embodiment E1 to E18, wherein R¹And R¹²Independently selected from Methyl, trifluoromethyl and 2,2,2- trifluoroethyls, wherein R¹And R¹²At least one of be trifluoromethyl or 2,2,2- trifluoroethyl.

E20. according to catalyst compounds one of any in embodiment E1 to E19, wherein each R^*1And R^*2It is independent Ground is selected from the substituted or unsubstituted group one of any comprising following formula:

Wherein C^*For the connection carbon of the group, and wherein the substituent group of each formula (i)-(xxiv) independently is hydrogen, C₁- C₄₀Alkyl, functional group, electron-withdrawing group or their combination comprising the element from periodic table of elements 13-17 race.

E21. according to catalyst compounds one of any in embodiment E1 to E20, wherein each R^*1And R^*2It is identical.

E22. it according to catalyst compounds one of any in embodiment E1 to E21, is expressed from the next:

And/or wherein catalyst compounds are expressed from the next:

Wherein R²To R⁶, R¹³To R¹⁷, R^*1And R^*2As defined above.

E23. according to the catalyst compounds of embodiment E22, wherein each X¹And X²For C₁-C₇Alkyl or benzyl.

E24. the catalyst compounds one of any according to embodiment E22 or E23, wherein each R¹、R²、R³、R⁴、R⁵、 R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, halogen or C₁-C₃₀Alkyl.

E25. according to catalyst compounds one of any in embodiment E22 to E24, wherein each R¹、R²、R³、R⁴、 R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, halogen or C₁-C₁₀Alkyl.

E26. according to catalyst compounds one of any in embodiment E22 to E25, wherein R^*1And R^*2In at least it One independently includes aromatics or part aromatic ring system.

E27. according to catalyst compounds one of any in embodiment E22 to E26, wherein R^*1And R^*2In at least it One independently includes at least one hexa-atomic aromatic ring.

E28. according to catalyst compounds one of any in embodiment E22 to E27, wherein R^*1And R^*2In at least it One independently includes indenyl ring system or fluorenyl ring system.

E29. according to catalyst compounds one of any in embodiment E22 to E28, wherein each R⁷For C₁-C₁₂Rouge Race's group or phenyl, preferably tert-butyl or phenyl.

E30. it according to catalyst compounds one of any in embodiment E1 to E29, is expressed from the next:

Wherein R¹To R¹⁷, R^*1And R^*2As defined above, and wherein each R³⁹And R⁴⁰It independently is hydrogen, C₁-C₄₀Alkyl, packet Functional group containing the element from periodic table of elements 13-17 race, R³⁹And R⁴⁰It is joined together to form C₄-C₆₂It is cyclic annular or polycyclic Ring structure or their combination.

E31. it according to catalyst compounds one of any in embodiment E1 to E29, is expressed from the next:

Wherein R²To R¹¹, R¹³To R¹⁷, R^*1And R^*2As defined above, and wherein each R⁴¹、 R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、 R⁴⁷、R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、R⁵³And R⁵⁴It independently is hydrogen, C₁-C₄₀Alkyl, comprising coming from periodic table of elements 13-17 race Element functional group, in two or more R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷、R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、 R⁵³With R⁵⁴It is separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure；Or their combination.

E32. following formula indicate catalyst compounds:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Y is divalent C₁-C₂₀Alkyl.

E33. following formula indicate catalyst compounds:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、 R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、 R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸It independently is hydrogen, C₁-C₄₀Alkyl, comprising coming from periodic table of elements 13-17 race Element functional group, R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、 R²⁷、R²⁸、R²⁹、 R³⁰、R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸In two or more be separately attached to be formed together C₄-C₆₂It is cyclic annular Or polycyclic ring structure or their combination；

Y is divalent C₁-C₂₀Alkyl.

E34. according to the catalyst compounds of embodiment E33, in which:

M is Zr or Hf；

X¹And X²For benzyl；

R¹、R⁵、R⁷、R¹²、R¹⁶And R¹⁸For methyl；

Y is ethylidene (- CH₂CH₂-)。

E35. it according to the catalyst compounds of embodiment E33, is indicated by one of following formula:

E36. catalyst system, it includes activator and according to catalyst one of any in embodiment E1 to E35 Close object.

E37. according to the catalyst system of embodiment E36, wherein the catalyst compounds, the activator or more than The two is all placed on carrier or in carrier.

E38. according to the catalyst system of embodiment E36 or E37, wherein the carrier includes comprising the 2nd, 4,13 or 14 The inorganic oxide material of family metal oxide.

E39. according to the catalyst system of embodiment E37, wherein the carrier includes Al₂O₃, ZrO₂, SiO₂, SiO₂/ Al₂O₃, finely divided functionalised polyolefin or their combination.

E40. catalyst system includes:

The catalyst compounds that activator and following formula indicate:

Wherein M is the 3rd, 4,5 or 6 group 4 transition metals；

N¹And N²For nitrogen；

O is oxygen；

Wherein C^*Indicate the connection carbon of the group；

Y is divalent C₁-C₂₀Alkyl.

E41. according to the catalyst system of embodiment E40, wherein each R^*1And R^*2It independently include replacing or not taking The cyclopentadienyl group and R in generation^*1And R^*2One of them independently includes the substituted or unsubstituted cyclopentadiene that following formula indicates Base:

Wherein C^*Indicate the connection carbon of the group；

Wherein each R¹⁸、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, C₁-C₄₀Alkyl, comprising from the periodic table of elements the The functional group of the element of 13-17 race, R¹⁹、R²⁰、R²¹And R²²In two or more be separately attached to be formed together C₄-C₆₂ Cyclic annular or polycyclic ring structure or their combination.

E42. according to the catalyst system of embodiment E40, wherein R^*1And R^*2At least one of independently include replace Or unsubstituted C₄-C₂₀Aliphatic series or alicyclic group.

E43. according to the catalyst system of embodiment E40, wherein R^*1And R^*2At least one of independently include inhale electricity Sub- functional group comprising-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,-SO₃H ,-COOH ,-CHO ,-F ,-Cl ,-Br ,-I ,- COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination, wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl.

E44. a kind of method, including make one or more alkene with according to one of any in embodiment E36 to E43 Caltalyst is tied up at the temperature, pressure and time for being enough to generate polyolefin and is contacted.

E45. the method for embodiment E44 according to, wherein activator include aikyiaiurnirsoxan beta, the aikyiaiurnirsoxan beta of modification, it is noncoordinating or The anion or their combination of weak coordination.

E46. according to the method for embodiment E44 or E45, wherein activator is the activator of poor trimethyl aluminium.

E47. according to method one of any in embodiment E44 to E46, wherein minimum activator and catalyst compounds The molar ratio of object is about 1:1- about 500:1.

E48. according to method one of any in embodiment E44 to E47, comprising being lower than 0.001wt% aikyiaiurnirsoxan beta.

E49. polyolefin, by being obtained according to method one of any in embodiment E44 to E48.

E50. according to the polyolefin of embodiment E49, including Mw is at least ethene polymers of 500,000g/mol.

E51. according to the polyolefin of embodiment E49, the propylene polymerization for being at least 90% including isotacticity Object.

E52. according to polyolefin one of any in embodiment E49 to E51, including isotacticity is at least 95% acrylic polymers.

E53. according to polyolefin one of any in embodiment E49 to E52, the Mw having is at least 500,000g/ Mol, or at least 800,000g/mol, or at least 1,000,000 g/mol, or at least 1,200,000g/mol, or At least 1,500,000g/mol.

E54. according to polyolefin one of any in embodiment E49 to E53, the Mw/Mn having be greater than 1-40, or Person 1.2-20 perhaps 1.3-10 perhaps 1.4-5 perhaps 1.5-4 or 1.5-3.

E55. according to polyolefin one of any in embodiment E49 to E54, including monomer include replacing or not taking The C in generation₂-C₄₀Alhpa olefin or C₂-C₂₀Alhpa olefin or C₂-C₁₂Alhpa olefin perhaps ethylene perhaps propylene perhaps butylene or Amylene perhaps hexene perhaps heptene perhaps octene perhaps nonene perhaps decene perhaps endecatylene or dodecylene, Or their combination.

E56. according to polyolefin one of any in embodiment E49 to E55, wherein the monomeric olefin it is nervous or not Nervous；

Wherein the monomeric olefin is monocycle shape or polycyclic,

Wherein the monomeric olefin includes hetero atom,

Wherein the monomeric olefin includes one or more functional groups,

Or their combination.

E57. a kind of mechanograph, it includes according to polyolefin one of any in embodiment E49 to E56.

E58. a kind of film, it includes according to polyolefin one of any in embodiment E49 to E56.

E59. a kind of adhesive-bonded fabric and/or fiber, it includes according to polyene one of any in embodiment E49 to E56 Hydrocarbon.

Embodiment

It is discussed above to be described with further reference to following non-limiting embodiment.Synthesized according to described a kind of or The example catalyst compound of multiple embodiments is simultaneously used for olefin polymerization.All reactions are all under the nitrogen atmosphere of purifying It is carried out using standard glove box, high vacuum or Schlenk technology, unless otherwise indicated.All solvents used are all according to Perception method is anhydrous, deoxidation and purification.All starting materials or go out purchased from Aldrich and in use premise, or According to method known to those skilled in the art preparation.Deuterated solvents are obtained from Cambridge Isotope Laboratories (Andover, MA) is used in combinationMolecular sieve is dry.For all material, own¹H NMR data is all Tetrachloroethanes-d is being used in room temperature (~25 DEG C)₂As solvent (chemical deviation of 5.98ppm is used as reference) operation Topspin^TMIt is collected on the Broker AVANCE III 400MHz spectrometer of 3.0 softwares.

The synthesis of compound A (CAT A):

The synthesis (1) of 9- methyl-9 H-fluorene -9- alcohol

In glove box, in 50mL round-bottomed flask, 9H- fluorenes -9- ketone (5.458g, 30.3mmol) is dissolved in 20mL's In THF and it is cooled to 0 DEG C 30 minutes.Then MeMgBr (1.2eq.) is slowly added to via needle tubing under stiring.In whole lattice Woods receive reagent be added after slurry formed.By reaction stirring 48 hours.Then flask is taken out to from glove box and is added the 2M of 4mL NaOH.Mixture is washed with brine, collects organic moiety, and use MgSO₄It dries, filters, and in N₂Volatilization is removed under air-flow Object.The NMR of gained yellow solid is shown as pure 9- methyl-9 H-fluorene -9- alcohol.Yield is 5.67g (95wt%).

The synthesis (2) of 4- methyl -2- (9- methyl-9 H-fluorene -9- base) phenol

In 200mL round-bottomed flask, paracresol (2.075g, 19.2mmol) and 2 (3.766g, 19.2mmol) are dissolved in The CH of 80mL₂Cl₂In.By the dense H of 4mL₂SO₄(5eq.) is added drop-wise to the solution under stiring, generates mulberry solution.Two hours Afterwards, which is slowly added to the H of l00 mL₂In O, white/blue precipitating is formed.Then 2M Na0H is added dropwise, until pH Reach 9-10.Then CH is used₂Cl₂(3x100mL) filtering stock.Then organic moiety is collected, and uses MgSO₄It is dry.In N₂Under Volatile matter is removed, brown residue is obtained.Products therefrom is used to the EtOAc/ hexane of 5-10% gradient on silica column Purification.

6,6 '-(ethane -1,2- diyl is bis- (methyl azane diyl)) bis- (ethylidene) are double) 4- methyl -2- (9- methyl - 9H- fluorenes -9- base) phenol synthesis (3)

In 100mL round-bottomed flask, by 2 (0.512g, 1.8mmol), N¹,N²Dimethyl ethane -1,2- diamines (0.079g, 0.9mmol) and formaldehyde (0.268g, 8.9mmol) are dissolved in the ethyl alcohol of 30mL.Flask is placed in oil bath and is added Heat reflux 16 hours.By ethyl alcohol in N₂It is removed under air-flow, obtains yellow oil.Product is used on silica column CH₂Cl₂The purification of/hexane.

[6,6 '-(ethane -1,2- diyl is bis- (methyl azane diyl)) bis- (ethylidene) are double) 4- methyl -2- (9- methyl - 9H- fluorenes -9- base) phenolate] dibenzyl zirconium (IV) synthesis (4)

In the vial, 3 (0.152g, 0.22mmol) are dissolved in 5mL toluene.In another bottle, by Zr (Bn)₄ (0.101g, 0.22mmol) is dissolved in 5mL toluene.Zirconium solution is added to ligand solution under stiring and is stirred 1 hour.Then Toluene is removed, yellow/orange residue is obtained.By the residue, the pulp in pentane, is then filtered, obtain yellow solid and Orange filtrate.The yield of yellow solid (4) is 0.153g (73wt%).

The synthesis of compound B (CAT B):

CAT B is prepared as above-mentioned CAT A, but uses Hf (Bn)₄Instead of Zr (Bn)₄。

The general steps of olefinic polymerization

Interval olefinic polymerization polymerize in test (HTPT) device in Parr bullet reactor in high yield to be referred in each table The catalyst (CAT A) of zirconium embodiment or the catalyst (CAT B) and activator of hafnium embodiment are used under conditions of out It carries out.Then resulting polymers are characterized by NMR.Data are shown in table 1, in 2,3 and 4.MAO indicates methylaluminoxane.D4 is indicated DMAH- perfluorophenyl boron activator (4).

It is provided in tables 1 and 2 with and without the vinyl polymerization result under 1- octene co-monomer.Propylene polymerization result To thick in table 3 and 4.

1. vinyl polymerizations of table-Zr catalyst (CAT A)

It is all to be aggregated in HTPT using 0.02 μm of ol (CAT A) with 500 equivalent MAO progress.

2. vinyl polymerizations of table-hafnium catalyst (CAT B)

It is all to be aggregated in HTPT using 0.02 μm of ol (CAT B) with 500 equivalent MAO at 100 DEG C.

3. propylene polymerizations of table-Zr catalyst (CAT A)

It is all to be aggregated in HTPT using 0.02 μm of ol (CAT A) with 1.1 equivalent D4.

4. propylene polymerizations of table-hafnium catalyst (CAT B)

It is all to be aggregated in HTPT using 0.02 μm of ol (CAT B) with 1.1 equivalent D4.

The preparation of isotactic polypropylene

Parr bullet and vial are chilled to -85 DEG C.By dry MAO (376mg, 6.l6mmol) and (CAT A) The vial is added in (11.2mg, 0.0117mmol).The propylene (20.5 g, 487mmol) of condensation is poured into the bottle, then by bottle It is sealed in Parr bullet.The bullet is heated at most 70 DEG C in oil bath and is stirred 1 hour.Then the bullet is taken out from oil bath, It leaks and opens.Polyacrylic yield is 11.058g.Activity: 944g polymer/(mmol cat*hr).The polypropylene is height It spends isotactic, shows as shown in figure 1¹Shown in H H NMR spectroscopy.

These statistics indicate that, catalyst compounds, catalyst system and polymerization disclosed herein, which can be prepared, to be had Improved property, such as high polymer fusing point, high polymer molecular weight, the conversion ratio of raising and/or comonomer incorporation it is poly- Close object.

The document being described herein is all incorporated by reference, including any priority document and/or test procedure, The degree of introducing will not be inconsistent with the text, however, condition is, it is any not mentioned in earlier application or in presenting a paper Priority document be not totally incorporated herein by reference.Although such as from aforementioned general description and specific embodiment it will be evident that originally The form of invention, which has been carried out, to be illustrated and described, but can make various remodeling without departing from the spirit and scope of the invention. Therefore, it is not intended to limit the present invention to foregoing illustrations and descriptions.Similarly, for the purpose of Australian law, term "comprising" is considered as the synonym of term " includes ".Similarly, there is conjunctive phrase " packet before component, element or one group of element Containing " when, it should be appreciated that also contemplated have before identical component or one group of element conjunctive phrase "consisting essentially of ...", " Consists of ", " selected from by ... the group formed " or "Yes" modify the component, element or one group of element, and vice versa.

Claims

1. the catalyst compounds that following formula indicates:

Wherein each solid line, which indicates covalent bond, and each arrow indicates has different degrees of valence state and different degrees of coordination Key；

Wherein M is the 4th group 4 transition metal；

N¹And N²For nitrogen；

O is oxygen；

Each X¹And X²It independently is monovalent C₁-C₂₀Alkyl, halogen, O, S, Se, Te, Or their combination, wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide electricity Neutral part or X¹And X²It is joined together to form C₄-C₆₂Cyclic annular or polycyclic ring structure, but condition is the X when M is trivalent² It is not present；

Wherein each R^*1And R^*2It independently include the function that molecular dimension is greater than or equal to the molecular dimension of isopropyl group part Group, electron-withdrawing group or their combination, and wherein R^*1And R^*2At least one of independently include having following structure Cyclopentadienyl group:

Wherein C^*Indicate the connection carbon of the group；

Each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, C₁-C₄₀Alkyl, Halogen, O, S, Se, Te, It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide the part of electroneutral, R¹、R²、R³、 R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination；

R⁷For C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein each It independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide the part of electroneutral；And

Y is divalent C₁-C₂₀Alkyl.

2. catalyst compounds according to claim 1, wherein each R^*1And R^*2It independently include substituted or unsubstituted Cyclopentadienyl group, and wherein R^*1And R^*2One of independently include following formula indicate substituted or unsubstituted cyclopentadienyl group:

Wherein C^*Indicate the connection carbon of the group；

Wherein each R¹⁸、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable Integer is to provide the part of electroneutral, R¹⁹、R²⁰、R²¹And R²²In two or more be separately attached to be formed together C₄-C₆₂ Cyclic annular or polycyclic ring structure or their combination.

3. catalyst compounds according to claim 1 or 2, wherein R^*1And R^*2At least one of independently include replace or Unsubstituted C₄-C₂₀Aliphatic group or C₄-C₂₀Alicyclic group.

4. catalyst compounds according to claim 1 or 2, wherein R^*1And R^*2At least one of independently include electrophilic Functional group, the electron attractive functional group include-NO₂,-CF₃,-CCl₃,-CBr₃,-CI₃,-CN ,-SO₃H ,-COOH ,-CHO ,-F ,- Cl ,-Br ,-I ,-COOR^α,-COR^α,-NR^α ₃ ⁺Or their combination, wherein each R^αIt independently is hydrogen or C₁-C₂₀Alkyl.

5. catalyst compounds according to claim 1 or 2, wherein R^*1And R^*2At least one of independently include hexa-atomic virtue Ring.

6. catalyst compounds according to claim 1 or 2, wherein R⁸And R⁹, R¹⁰And R¹¹, R when it is present¹⁹With And R²⁰, and R when it is present²¹And R²²Middle at least one set is separately attached to be formed together at least one hexa-atomic aromatic ring.

7. catalyst compounds according to claim 1 or 2, wherein R⁸And R⁹And/or R¹⁰And R¹¹It is independently connected Indenyl ring system or fluorenyl ring system are formed together；

Wherein R when it is present¹⁹And R²⁰, and/or R when it is present²¹And R²²It is separately attached to be formed together indenyl rings System or fluorenyl ring system or their combination.

8. catalyst compounds according to claim 1 or 2, wherein each R when it is present⁷And R¹⁸It independently is C₁-C₁₂ Aliphatic group or phenyl.

9. catalyst compounds according to claim 1 or 2, wherein Y is bivalent cyclic, branch or straight chain C₁-C₁₂Alkyl.

10. catalyst compounds according to claim 1 or 2, wherein Y is selected from methylene, ethylidene, propylidene, Aden Base, pentylidene, hexylidene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, cyclohexylidene, phenylene and Benzal.

11. catalyst compounds according to claim 1 or 2, wherein Y is ethylidene-CH₂CH₂, 1,3- propylidene-CH =CHCH₂, 1,2- cyclohexylidene, 1,2- phenylene or 2- benzal.

12. catalyst compounds according to claim 1 or 2, wherein M is Hf, Ti or Zr.

13. catalyst compounds according to claim 1 or 2, wherein each X¹And X²It independently is halogen or C₁-C₇Hydrocarbon Base.

14. catalyst compounds according to claim 1 or 2, wherein each X¹And X²For benzyl.

15. catalyst compounds according to claim 1 or 2, wherein each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、 R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, halogen or C when it is present₁-C₃₀Alkyl.

16. catalyst compounds according to claim 1 or 2, wherein each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、 R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、R²⁰、R²¹And R²²It independently is hydrogen, halogen or C when it is present₁-C₁₀Alkyl.

17. catalyst compounds according to claim 1 or 2, wherein R¹And R¹²Independently selected from methyl and end position halogen Substituted C₁-C₄Alkyl.

18. catalyst compounds according to claim 1, wherein R¹And R¹²It independently is tri- halogen second of haloform or 2,2,2- Alkane.

19. catalyst compounds according to claim 18, wherein R¹And R¹²It independently is fluoroform or 2,2,2- trifluoro second Alkane.

20. catalyst compounds according to claim 1 or 2, wherein R¹And R¹²Independently selected from methyl, trifluoromethyl and 2,2,2- trifluoroethyls, wherein R¹And R¹²At least one of be trifluoromethyl or 2,2,2- trifluoroethyl.

21. catalyst compounds according to claim 1 or 2, wherein each R^*1And R^*2Independently selected from include following formula appoint The substituted or unsubstituted group of one of meaning:

Wherein C^*For the connection carbon of the group, and wherein the substituent group of each formula (i)-(xxiv) independently is hydrogen, C₁-C₄₀Hydrocarbon Base, halogen, O, S, Se, Te, It is wherein each It independently is hydrogen or C₁-C₂₀Alkyl, wherein x be suitable integer with provide the part of electroneutral, electron-withdrawing group or they Combination.

22. catalyst compounds according to claim 1 or 2, wherein each R^*1And R^*2It is identical.

23. catalyst compounds according to claim 1 or 2, wherein R¹For methyl and R¹²For-CH₂-CF₃。

24. catalyst compounds according to claim 1 or 2, wherein R¹And R¹²It is all-CH₂-CF₃。

25. according to the catalyst compounds of claim 23 or 24, wherein each X¹And X²For C₁-C₇Alkyl or benzyl.

26. according to the catalyst compounds of claim 23 or 24, wherein each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、 R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, halogen or C₁-C₃₀Alkyl.

27. according to the catalyst compounds of claim 23 or 24, wherein each R¹、R²、R³、R⁴、R⁵、R⁶、R⁸、R⁹、R¹⁰、R¹¹、 R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶And R¹⁷It independently is hydrogen, halogen or C₁-C₁₀Alkyl.

28. according to the catalyst compounds of claim 23 or 24, wherein R^*1And R^*2At least one of independently include aromatics or Part aromatic ring system.

29. according to the catalyst compounds of claim 23 or 24, wherein R^*1And R^*2At least one of independently include at least one A hexa-atomic aromatic ring.

30. according to the catalyst compounds of claim 23 or 24, wherein R^*1And R^*2At least one of independently include indenyl rings System or fluorenyl ring system.

31. according to the catalyst compounds of claim 23 or 24, wherein each R⁷For C₁-C₁₂Aliphatic group or phenyl.

32. according to the catalyst compounds of claim 23 or 24, wherein each R⁷For tert-butyl or phenyl.

33. catalyst compounds according to claim 1 or 2, are expressed from the next:

Wherein each R³⁹And R⁴⁰It independently is hydrogen, C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide electroneutral Part, R³⁹And R⁴⁰It is joined together to form C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.

34. catalyst compounds according to claim 1 or 2, are expressed from the next:

Wherein each R⁴¹、R⁴²、R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷、R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、R⁵³And R⁵⁴It independently is hydrogen, C₁-C₄₀Hydrocarbon Base, halogen, O, S, Se, Te,

It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide the part of electroneutral, R⁴¹、R⁴²、 R⁴³、R⁴⁴、R⁴⁵、R⁴⁶、R⁴⁷、R⁴⁸、R⁴⁹、R⁵⁰、R⁵¹、R⁵²、R⁵³And R⁵⁴In two or more be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination.

35. catalyst compounds according to claim 1 or 2, are expressed from the next:

Wherein

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、R²⁰、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、 R²⁹And R³⁰It independently is hydrogen, C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x be Suitable integer is to provide the part of electroneutral, R¹、R²、R³、R⁴、R⁵、R⁶、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁹、 R²⁰、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹And R³⁰In two or more be separately attached to be formed together C₄-C₆₂It is cyclic annular or Polycyclic ring structure or their combination；

Each R⁷And R¹⁸It independently is C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein eachIt independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide the part of electroneutral, or Their combination；And

Y is divalent C₁-C₂₀Alkyl.

36. catalyst compounds according to claim 1 or 2, are expressed from the next:

Wherein

Each R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、R³¹、R³²、 R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸It independently is hydrogen, C₁-C₄₀Alkyl, halogen, O, S, Se, Te, It is wherein each It independently is hydrogen or C₁-C₂₀Alkyl, wherein x is suitable integer to provide the part of electroneutral, R¹、R²、R³、R⁴、R⁵、R⁶、R¹²、 R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸In two It is a or more to be separately attached to be formed together C₄-C₆₂Cyclic annular or polycyclic ring structure or their combination；

Y is divalent C₁-C₂₀Alkyl.

37. catalyst compounds according to claim 36, in which:

M is Zr or Hf；

X¹And X²For benzyl；

R¹、R⁵、R⁷、R¹²、R¹⁶And R¹⁸For methyl；

R²、R³、R⁴、R⁶、R¹³,R¹⁴、R¹⁵、R¹⁷、R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰、R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷ And R³⁸For hydrogen；And

Y is ethylidene-CH₂CH₂-。

38. catalyst compounds according to claim 36 are indicated by one of following formula:

39. catalyst system, it includes activator and according to claim 1 to catalyst compounds described in any one of 38.

40. catalyst system according to claim 39, the wherein catalyst compounds, the activator or both of the above It is all placed on carrier or in carrier.

41. catalyst system according to claim 40, wherein the carrier includes comprising the race of the 2nd, 4,13 or 14 metal oxygen The inorganic oxide material of compound.

42. the catalyst system according to claim 40 or 41, wherein the carrier includes Al₂O₃, ZrO₂, SiO₂, SiO₂/ Al₂O₃, finely divided functionalised polyolefin or their combination.

43. a kind of method for preparing polyolefin, including make one or more alkene with according to claim any one of 39-42 Caltalyst tie up at the temperature, pressure and time for being enough to generate polyolefin and contact.

44. according to the method for claim 43, wherein activator include aikyiaiurnirsoxan beta, it is the aikyiaiurnirsoxan beta of modification, noncoordinating or weak The anion or their combination of coordination.

45. the method according to claim 43 or 44, wherein activator is the activator of poor trimethyl aluminium.

46. the method according to claim 43 or 44, wherein the molar ratio of minimum activator and catalyst compounds is 1: 1-500:1.

47. the method according to claim 43 or 44, the aikyiaiurnirsoxan beta comprising being lower than 0.001wt%.